CN106622329B - The method of two-dimentional nitrogen-doped graphene is prepared in the microreactor of vertical direction confinement - Google Patents
The method of two-dimentional nitrogen-doped graphene is prepared in the microreactor of vertical direction confinement Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011229 interlayer Substances 0.000 claims abstract description 57
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 31
- 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 23
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 22
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- DPZVOQSREQBFML-UHFFFAOYSA-N 3h-pyrrolo[3,4-c]pyridine Chemical compound C1=NC=C2CN=CC2=C1 DPZVOQSREQBFML-UHFFFAOYSA-N 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000003780 insertion Methods 0.000 claims description 8
- 230000037431 insertion Effects 0.000 claims description 8
- 229920002521 macromolecule Polymers 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
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims 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 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
- 238000003483 aging Methods 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 238000006479 redox reaction Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 14
- 239000003990 capacitor Substances 0.000 abstract description 12
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract description 7
- -1 Alkyl dimethyl benzyl ammonium bromide Chemical compound 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- 229910052901 montmorillonite Inorganic materials 0.000 description 16
- 230000033116 oxidation-reduction process Effects 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 10
- 229920000767 polyaniline Polymers 0.000 description 10
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229920002480 polybenzimidazole Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 229920000137 polyphosphoric acid Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 229920000128 polypyrrole Polymers 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
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 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
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture 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
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-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
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000009825 accumulation Methods 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 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
- 239000000203 mixture Substances 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
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation 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
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer 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
- 238000012546 transfer Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing 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 present invention is the method that two-dimentional nitrogen-doped graphene is prepared in the microreactor of vertical direction confinement.The microreactor of vertical direction confinement is to use C4~C16The hydrophobic stratified material of Alkyl dimethyl benzyl ammonium bromide modified montmorillonoid is template, and injecting poly- (2,5- benzimidazole) (ABPBI) with vacuum aided method in the hydrophobic interlayer is carbon source and nitrogen source.Benzimidazole ring in its ABPBI molecule regularly in template interlayer, is pyrolyzed, remove template agent removing after obtain the N doping two-dimensional graphene of high nitrogen-containing.ABPBI, which is selected, can dissolve oligomer；Distance between stratiform template interlayer is adjusted by size of cationic surfactant alkyl chain of its absorption etc., and interlamellar spacing is between 0.2~0.6 nm；ABPBI and stratiform template mass ratio are 2:1~1:3；Pyrolysis temperature is 700 ~ 1100 DEG C.Catalyst, the fields such as electrode material for super capacitor are precipitated for fuel cell or the oxygen reduction catalyst of metal air battery cathodes, the oxygen of anode of electrolytic water in the high nitrogen-containing two dimension nitrogen-doped graphene of preparation.
Description
Technical field
Belong to field of nano material preparation, is urged for the fuel cell in clean energy resource field, the cathode of metal-air battery
Agent, electrolysis water catalyst, the fields such as electrode material for super capacitor and electrochemical sensor.
Background technique
Graphene is the single layer two dimension carbonaceous material being made of carbon atom, due to fabulous electricity, optics, machinery etc.
Performance and the attention (Bacsa R R, et al. Carbon (carbon), 2015,89:350) of people.Hetero atom (e.g., N, P,
B and S etc.) the graphene performance after doping is more prominent, can also be adulterated with codope or three 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
Have oxygen reduction activity (Nie Yao etc., Journal of Chemical Industry and Engineering), 2015,66:3305), on the contrary, the nitrogen-atoms of three-dimensional structure is not lived
Property.The method for preparing nitrogen-doped graphene has: graphite oxide reduction method, the heat-treatment oxidation graphene (Li under ammonia atmosphere
X, et al. J Am Chem Soc(American Chemical Society) 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-pyridine (Zhao Y, the et al. J Am Chem Soc (American Chemical Society of Fe, Co coordination polymerization abundant
Will), 2012,134 (48): 19528)；It is three-dimensional for the reduction preparation of template ethylenediamine in silica etc. with graphene oxide
The nitrogen-doped graphene of structure have 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, synthesized, the two-dimentional nitrogen-doped graphene for being pyrolyzed preparation can be containing more
Pyridine nitrogen and pyrroles's nitrogen show excellent catalytic oxidation-reduction performance.The method of document is that template montmorillonite is changed using acid
Property preparation H+The montmorillonite of type obtains the interlayer of hydrophilic；It is the aniline that small molecule aniline generates hydrophilic in acid condition
Hydrochloride is conducive to be inserted into the interlayer of hydrophilic, and small molecule is also easy to enter in interlayer, does not need to carry out complicated operation；
Polymerization reaction occurs in interlayer for aniline, obtains polyaniline, and the process of polymerization is just controlled by vertical direction area size.?
The molecule of the polyaniline plane arrived, is pyrolyzed under inert gas protection, obtains the graphene of two-dimentional N doping.
The present invention is the high molecular material for utilizing the benzimidazole unit of armaticity, poly- (2,5- benzimidazole) (ABPBI)
For carbon source and nitrogen source, pyrolysis prepares the carbon material of N doping under inert gas protection.It is covered with cationic surfactant is modified
De- soil stratified material, obtains hydrophobic interlayer and does template, keep rigid ABPBI molecule regularly arranged in interlayer, does not occur a large amount of
Stacking, curling etc. are unfavorable for the case where generating graphene, to prepare the material of multilayer two-dimension nitrogen-doped graphene structure.The present invention
It is with document difference: firstly, will be to the sour modification of stratiform mould material, to increase interlamellar spacing and cation easily in positive
Ionic surface active agent replaces.It is modified processing with cationic surfactant again, so that its interlayer is become hydrophobic, and layer
Spacing becomes larger, and so that it is conducive to hydrophobic high molecular material and is inserted into interlayer；Secondly, the method using vacuum aided makes high score
Sub- ABPBI molecule can enter in interlayer；Third, the ABPBI molecule of rigidity dry rule that can achieve molecule in interlayer
Arrangement is beneficial to prevent a large amount of stackings, curling etc. and is unfavorable for the case where generating graphene.It is protected after being inserted into ABPBI in inert gas
The lower pyrolysis of shield, goes template agent removing that the graphene of two-dimentional N doping can be obtained.
And the method for document is template montmorillonite using the modified preparation H of acid+The montmorillonite of type obtains the folder of hydrophilic
Layer；Small molecule aniline generates water-soluble anilinechloride in acid condition, is conducive to be inserted into the interlayer of hydrophilic；Again
Person, small molecule are also easy to enter in interlayer, do not need to carry out complicated operation；Polymerization reaction occurs in interlayer for aniline, obtains
The process of polyaniline, polymerization is just controlled by area size.The molecule of obtained polyaniline plane, in inert gas shielding
Lower pyrolysis, obtains the graphene of two-dimentional N doping.
Key technology of the invention is the silicic acid anhydride of interlayer, the control of interlamellar spacing, the insertion of ABPBI molecule and rule
The factors such as the proportion of arrangement and ABPBI and template.Hydrophobic treatment is the basis of macromolecule insertion, interlamellar spacing control and template
Agent and ABPBI proportion decide the regular degree of macromolecule arrangement and obtain the number of plies of graphene.
Poly- 2,5- benzimidazole (ABPBI) is simplest one kind in PBI family, is using 3,4- diaminobenzoic acid
Raw material, under nitrogen protection, condensation polymerization is made under the conditions of 200 DEG C in polyphosphoric acids (PPA).It prepares reaction equation such as
Under:
Polybenzimidazoles (PBI) is a kind of high molecular polymer containing benzimidazole group, benzimidazole ring in molecule
The stiffening ring for belonging to armaticity, the easily accumulation aggregation in PBI molecule.
The invention is using the benzimidazole of armaticity as the raw material of offer carbon and nitrogen, under inert gas argon gas shielded
Pyrolysis prepares nitrogenous carbon material.PBI solution is pressed between the interlayer of hydrophobic stratified material by the method for vacuum aided,
Solvent is removed in vacuo, keeps 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 limit its reaction, can form two-dimensional plane N doping in the horizontal direction
Graphene-structured goes template agent removing to obtain two-dimentional nitrogen-doped graphene.Change ratio, the control template interlamellar spacing of ABPBI and template
Come control preparation nitrogen-doped graphene the number of plies and performance, finally obtain ideal multilayer two-dimension nitrogen-doped graphene.
It is common method that high molecular material method for pyrolysis, which prepares carbon material, such as uses phenolic resin, pollopas and trimerization
The pyrolysis such as melamine resin prepare carbon material.Compared with the high molecular materials such as phenolic resin, pollopas and melamine resin,
ABPBI is the difference is that it contains the stiffening ring benzimidazole ring of armaticity, and the imidazoles nitrogen on imidazole ring contains it
Nitrogen quantity is more abundant.Therefore the carbon material of the N doping of the available high-content of high temperature pyrolysis ABPBI, and it is suitable by introducing
The orientation of the fragrant plane of a loop of template or control molecule and the limitation of vertical direction, available multilayer nitrogen is mixed after pyrolysis
Miscellaneous grapheme material.Compared with the high molecular materials such as polyaniline and polypyrrole, ABPBI be can dissolve, and be inserted easily into template
In interlayer, and polyaniline, polypyrrole etc. are insoluble, can not mix with template.
Summary 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 high molecular material of imidazole unit, poly- (2,5- benzimidazole) (ABPBI) are carbon source and nitrogen source, are changed with cationic surfactant
The montmorillonite layered material of property, obtains hydrophobic interlayer and does template, rigid hydrophobic ABPBI molecule is made to be inserted into hydrophobic interlayer, and
And it is regularly arranged in interlayer, it prevents a large amount of stackings, curling etc. and is unfavorable for the case where generating graphene, to prepare multilayer two
Tie up the material of nitrogen-doped graphene structure.By selecting the molecular structure of cationic surfactant, regulate and control hydrophobic interlayer interlayer
Away from the number of plies for the nitrogen-doped graphene that further prepared by regulation.The mass ratio and raw material for controlling raw material and template are inserted into interlayer
Method control arrangement mode of the ABPBI molecule in interlayer, and then control the quality and performance for generating nitrogen-doped graphene.
The present invention is with document difference: firstly, will be to the sour modification of stratiform mould material, to increase interlamellar spacing.
It is modified processing with cationic surfactant again, so that its interlayer is become hydrophobic, and interlamellar spacing becomes larger, passes through adjusting
The alkyl chain of cationic surfactant adjusts the interlamellar spacing of interlayer, so that it is conducive to hydrophobic high molecular material and is inserted into folder
In layer, and it is regularly arranged.Cationic surfactant selects C4~C16Alkyl dimethyl benzyl ammonium bromide etc.；Secondly, using vacuum
The method of auxiliary enters macromolecule ABPBI molecule in interlayer；Third, the method for vacuum aided and the hydrophobicity of interlayer can
So that the ABPBI molecule of rigidity reaches the regularly arranged of molecule when dry in interlayer, it is beneficial to prevent a large amount of stackings, curling etc.
It is unfavorable for the case where generating graphene generation.It is pyrolyzed under inert gas protection after insertion ABPBI, template agent removing is gone to can be obtained
The graphene of two-dimentional N doping.
And the method for document is template montmorillonite using the modified preparation H of acid+The montmorillonite of type obtains the folder of hydrophilic
Layer；Small molecule aniline generates water-soluble anilinechloride in acid condition, is conducive to be inserted into the interlayer of hydrophilic；Again
Person, small molecule are also easy to enter in interlayer, do not need to carry out complicated operation；Polymerization reaction occurs in interlayer for aniline, obtains
Polyaniline；And this method cannot 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 small, macromolecule be cannot be introduced into；ABPBI regular cannot be arranged under third free state
Column, under the conditions of vacuum aided and hydrophobic environment is conducive to the regularly arranged of ABPBI.Only regularly arranged ABPBI is in argon gas
A series of thermal chemical reactions such as dehydrogenation-cyclisation-carbonization occur under protection when pyrolysis could form nitrogen-doped graphene structure.
Key technology of the invention is the silicic acid anhydride of interlayer, the control of interlamellar spacing, the insertion of ABPBI molecule and rule
The factors such as the proportion of arrangement and ABPBI and template.Hydrophobic treatment is the basis of hydrophobic polymer insertion, cationic surface
The structure of activating agent can regulate and control the interlamellar spacing of interlayer.Template and ABPBI match and assist the insertion of ABPBI rigid macromolecule
Mode decides the regular degree of arrangement of the macromolecule in interlayer and obtains the number of plies and performance of graphene.
The interlamellar spacing of interlayer is adjusted by adjusting the alkyl chain of cationic surfactant, controls ABPBI and template
The methods of mass percent, the injection mode of ABPBI solution and pyrolytic process regulate and control the number of plies of the nitrogen-doped graphene of preparation.
The material be applied to fuel cell, metal-air battery Cathodic oxygen reduction catalyst, electrolysis water oxygen be precipitated catalyst and
Carrier, supercapacitor, the fields such as sensor material.
The high molecular materials such as ABPBI and the above phenolic resin, pollopas and melamine resin difference is: 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 available multilayer N doping.If
The plane for controlling the aromatic rings of molecule is arranged according to a direction, is pyrolyzed the graphene-structured of available N doping.With polyphenyl
Unlike the high molecular materials such as amine, poly- (o-phenylenediamine), polypyrrole: ABPBI class macromolecule is soluble in DMAc, DMSO etc.
In organic solvent, easily it is inserted into hydrophobic interlayer, due to its solubility, the tool when preparing nitrogen-doped graphene nano material
There is good operability.However, the high molecular materials such as polyaniline compound, polypyrrole are insoluble, can not be inserted into the interlayer of template.
ABPBI macromolecular chain is made of the rigid benzimidazole of armaticity, and contains the imidazole ring and end for being rich in nitrogen 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 N-Methyl pyrrolidone equal solvent.Molecular weight is too big, and the solubility property of ABPBI is deteriorated；Its too small 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 are as follows: montmorillonite carries out acidification first, cleans drying, respectively
The cationic surfactant that different alkyl chains are added is modified, and prepares the montmorillonite of hydrophobic interlayer as template.One
Quantitative template is put into the container that can be vacuumized, and a certain amount of ABPBI dissolution is formed solution in a solvent, wait fill
After 30 min of container vacuum-pumping of template, valve is closed, the solution of appropriate ABPBI is injected into container with syringe, to molten
It after liquid submerges template, begins to warm up, vacuumize, steam solvent at leisure and done to close, it is repeated multiple times in this way until ABPBI's is molten
Liquid is finished.It takes out, is dried at 60 ~ 120 DEG C in drying box.It is finely ground in mortar, it is laid in porcelain boat bottom, is put into electric tube furnace
It is interior, under protection of argon gas, at 700~1100 DEG C, it is pyrolyzed 2 ~ 3h.It is cooled to room temperature to furnace temperature, takes out, repeatedly washed with hydrofluoric acid
It washs to go removing template montmorillonite, filters, be washed with deionized water, dry, obtain two-dimentional nitrogen-doped graphene.
In the present invention: the optional quaternary ammonium surfactants of cationic surfactant: such as using C4~C16Alkyl dimethyl benzyl
Base ammonium bromide etc..The hydrophobicity that the length of its alkyl not only can control interlayer is strong and weak, and the interlamellar spacing of adjustable 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 determines
The amount of ABPBI can be injected, and then determines the number of plies of prepared graphene.In the case where ABPBI is inserted into sufficient situation, interlamellar spacing
Wider, ABPBI is inserted into more, and the number of plies of obtained graphene is also more.Therefore, the modification of cationic surfactant is very
It is important.Another key technology of the invention is filling and arranging situation of the ABPBI in interlayer: requiring ABPBI to fill first
Full interlayer；Secondly, it is desirable that ABPBI is regularly arranged in interlayer.It only in this way can just obtain complete two-dimentional nitrogen-doped graphene.
This requires ABPBI solution repeatedly to suck, and waiting a moment, it is multiple to drain rear repetitive operation slowly.
The mass ratio of ABPBI and template modified montmorillonoid is 2:1~1:3；Hybrid mode are as follows: weigh a certain amount of template
Agent modified montmorillonoid 160~220 DEG C of heating 2h in high temperature furnace adsorb water, gas or impurity to remove in multilayer material interlayer.
Room temperature to be cooled to, is transferred in the pressure vessel for being connected with vacuum pump, vacuumizes 30~40 min, with syringe into pressure vessel
A certain amount of ABPBI solution is injected, so that ABPBI solution is impregnated template, continues to vacuumize, after no liquid in container, is continued
Aforesaid operations run out up to ABPBI solution, drain.The template of sucking ABPBI solution, take out in vacuum oven
Interior 60~120 DEG C of ageings, drying is cooled to room temperature, finely ground, is put into porcelain boat, in high temperature furnace 700 ~ 1100 under argon gas protection
It is pyrolyzed 2~3h at DEG C, after furnace temperature is cooling, takes out sample, washes away template with hydrofluoric acid, acid is washed with deionized water, it is dry,
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 cannot be pyrolyzed, and be produced
The electric conductivity of product is poor；After pyrolysis temperature reaches optimum temperature, then to increase pyrolysis temperature its performance constant, so pyrolysis temperature is not
It is preferably excessively high.
The graphene characterizing method of two-dimentional N doping are as follows: aperture, porosity, Kong Rong and specific surface area nitrogen adsorption instrument
(BET), the Morphology analysis of product scanning electron microscope (SEM) and projection electron microscope (TEM), graphene number of plies
It can be characterized by high power transmission electron microscope (HRTEM).Degree of graphitization, graphene-structured and the number of plies of product can be with
It is characterized with X-ray powder diffraction (XRD), Raman spectrum.The element of product forms, and valence state can use X-ray photoelectron energy
Spectrum (XPS) is characterized, and reacts (ORR) performance, water power with rotating disk electrode (r.d.e) (RDE) come the catalytic oxidation-reduction of test product
It solves oxygen evolution reaction (EOR), the capacitive property test of evolving hydrogen reaction (EHR) and product can use cyclic voltammetric (CV), linear volt
Peace (LSV), Tafel curve and charge-discharge performance are tested.CV, LSV can be used as the durability test of catalyst in product
With chronoa mperometric plot (i-t).The catalytic performance of product finally needs to assemble metal-air battery, hydrogen-oxygen fuel cell, electrolysis
Electrolytic cell, supercapacitor and the sensor of water tests its performance.
Specific embodiment
The preparation (method one, solid phase method) of [embodiment 1] ABPBI: take suitable 3,4- diaminobenzoic acid (DABA) in
In mortar, it is transferred to after being fully ground equipped in electric stirring, inert gas shielding three-necked flask, logical nitrogen 15min is to arrange
Air to the greatest extent in flask.Nitrogen protection, under stirring, 225 DEG C of oil bath heating keep 3h.It is taken out after cooling, finely ground, nitrogen protection
Under, heating in electric furnace is warming up to 270-275 DEG C, keeps 3h.Be cooled to room temperature, by product take out, it is finely ground to get arrive ABPBI,
With the molecular weight of determination of ubbelohde viscometer ABPBI.
The preparation (method two, liquid phase method) of [embodiment 2] ABPBI: polyphosphoric acids (PPA) (50 g) is added to three
In mouth flask, under nitrogen protection, 160 DEG C of 1 h of stirring are to remove moisture and air.Addition 3,4- diaminobenzoic acid (6 g,
39.5 mmol) and temperature is increased at 200 DEG C is stirred to react 5 ~ 8 h, about 5 g P are added portionwise in reaction process2O5With
The water generated during absorbing reaction.With the increase in reaction time, polymerization system gradually becomes sticky.Reaction mixture is slowly
It is transferred in deionized water, reels off raw silk from cocoons, form fibrous black solid, take out drying, crush, wash to remove in reaction mixture
Polyphosphoric acids and unreacted raw material.Obtain ABPBI product.With the molecular weight of determination of ubbelohde viscometer ABPBI.
The sour modification of [embodiment 3] montmorillonite and cationic surfactant modification.
The acid of montmorillonite is modified: taking 10 g montmorillonites (Na-MMT) to be put into 1000mL beaker, 600 mL 0.1 are added
The HCl of mol/L under stirring, impregnates 2 days, filters, repeatedly washed, filtered with a large amount of deionized water, 60 DEG C of dry sour modifications
Montmorillonite (H-MMT).Measuring its ion exchange capacity is 0.25 meq/g.
Cationic surfactant C16Modified montmorillonite (the MMT of Alkyl dimethyl benzyl ammonium bromideC16B), weigh 5 g H-
MMT(0.25 meq/g), dry 2 h at 120 ~ 220 DEG C are slowly added under stiring with impurity such as the water that removes its absorption
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 that it is uniformly dispersed, stands overnight, filters, is cleaned with deionized water to no bromide ion, 120
It is dried at DEG C, grinds, obtain using C16The modified MMT brief note of Alkyl dimethyl benzyl ammonium bromide surfactant (being abbreviated as C16B)
For MMTC16B。
C can be carried out in aforementioned manners4~C15The illiteracy of the modification of Alkyl dimethyl benzyl ammonium bromide cationic surfactant
De- soil, is abbreviated as MMTCXB, wherein X is the carbon atom number of alkyl.
[embodiment 4] uses MMTC16BAs template, by taking ABPBI and template mass ratio are 1:1 as an example: in 250 mL
Beaker in, ten thousand) and 20 mL DMAc the ABPBI(viscosity average molecular weigh 1 ~ 3 that 1 g is added, is heated, is stirred to dissolve, and solution is taken out
Filter, it is spare to remove insoluble matter.In the bottle,suction of 250 mL for being connected with vacuum pump, 1 g MMT is addedC16BIt is laid in it
Bottom of bottle after vacuumizing 30 min, closes valve, stops vacuumizing, the DMAc solution of ABPBI is added with syringe, makes it sufficiently
Template is soaked, heating continues to vacuumize to remove solvent, after to be dried, repeat above operation, repeated multiple times until handle
The DMAc solution of ABPBI is all added, and after draining, takes out, is aged at 60~120 DEG C, and drying is finely ground to cold taking-up, is put into porcelain
Boat is pyrolyzed 2~3h at 800 DEG C under argon gas protection in high temperature furnace, cooling, takes out, is repeatedly washed with hydrofluoric acid, to remove removing template
Agent is washed with deionized water to neutrality, obtains 0.66 g of black powder solid in vacuum drying.BET test shows its surface
Product is 542 m2 g-1, aperture is 15 ~ 20 nm, and the product that SEM test shows is porous material, TEM and HRTEM analysis
Show that product is multi-layer graphene structural material, graphene is drawn a bow to the full back as 3 ~ 4 layers of graphene.XRD and Raman spectrum test show
The graphene-structured that product is 3 ~ 4 layers；XPS analysis shows 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 originates oxygen
Reduction potential is 0.98 V vs RHE, and electron transfer number 3.98, durability is good；Magnesium air battery performance is up to 112 mW/
cm2.It is 547 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen is precipitated take-off potential and is in the sulfuric acid solution of 0.5 mol/L
1.54 Vvs RHE, limiting current density reach 80 mA/cm2.Supercapacitor specific capacitance is 451 F/g, is recycled
10000 times still holding capacitor value 97%.
[embodiment 5] as described in Example 4, other conditions are identical, and only pyrolysis temperature is changed to 700 DEG C.Obtained production
Product are 0.70 g black powder, 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 lower, electronic conductivity is slightly worse, so its chemical property is slightly worse: it 0.1
In mol/L KOH solution, 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 battery performance is up to 64 mW/cm2.It is 219 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.64 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 40
mA/cm2.Supercapacitor specific capacitance be 252 F/g, be recycled 10000 times still holding capacitor value 94%.
[embodiment 6] as described in Example 4, other conditions are identical, only change pyrolysis temperature and are changed to 900 DEG C.It obtains
Product be 0.65 g black powder, test result shows that its product remains as 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.99 V vs RHE, electricity
Son transfer number is 3.98, and durability is good；Magnesium air battery performance is up to 116 mW/cm2.For its peak power of hydrogen-oxygen fuel cell
For 549 mW/cm2, it is 1.53 V vs RHE, limiting current density that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Reach 90 mA/cm2.Supercapacitor specific capacitance be 428 F/g, be recycled 10000 times still holding capacitor value 97%.
[embodiment 7] as described in Example 4, other conditions are identical, and only pyrolysis temperature is changed to 1100 DEG C.It obtains
Product is 0.60 g black powder, and test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Expect, in 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.93 V vs RHE, electronics
Shifting number is 3.87, and durability is good；Magnesium air battery 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 take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches
To 50 mA/cm2.Supercapacitor specific capacitance be 189 F/g, be recycled 10000 times still holding capacitor value 97%.
[embodiment 8] as described in Example 4, other conditions are identical, only change ABPBI and MMTC16BTemplate
Ratio is 1:2.Obtained product is 0.70 g black powder, 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 filling is not enough, obtained two-dimentional N doping
Graphene sheet layer becomes smaller, and electric conductivity is deteriorated, and in 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen starting is also
Former current potential is 0.90 V vs RHE, and electron transfer number 3.64, durability is good；Magnesium air battery performance is up to 81 mW/cm2。
It is 278 mW/cm for its peak power of hydrogen-oxygen fuel cell2.Oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.59 V vs RHE, limiting current density reach 60 mA/cm2.Supercapacitor specific capacitance is 346 F/g, is recycled
10000 times still holding capacitor value 94%.
[embodiment 9] as described in Example 4, other conditions are identical, only change ABPBI and MMTC16BTemplate
Ratio is 1:3.Obtained product is 0.71 g black powder, 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 filling is not enough, obtained two-dimentional nitrogen
Doped graphene lamella becomes smaller, and electric conductivity is deteriorated.In its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen is risen
Beginning reduction potential is 0.76 V vs RHE, and electron transfer number 3.57, durability is good；Magnesium air battery performance is up to 57 mW/
cm2.It is 187 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen is precipitated take-off potential and is in the sulfuric acid solution of 0.5 mol/L
1.66 vs RHE, limiting current density reach 40 mA/cm2.Supercapacitor specific capacitance is 236 F/g, is recycled 10000
The 93% of secondary still holding capacitor value.
[embodiment 10] as described in Example 4, other conditions are identical, only change ABPBI and MMTC16BTemplate
Ratio is 2:1.Obtained product is 0.67 g black powder, and test result shows its product in addition to 2 ~ 4 layers of two-dimentional N doping
Except the material of graphene-structured, there are also the carbon materials of part N doping.This is because the increase of ABPBI amount, so that ABPBI is removed
Except filling interlayer gap, there are also some residual, remaining ABPBI coats the porous carbon to form N doping on template surface
Material, catalytic performance are 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 3.55, durability is good；Magnesium air battery 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 take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
RHE, limiting current density reach 40 mA/cm2.Supercapacitor specific capacitance is 194 F/g, is recycled 10000 times and still keeps
The 90% of capacitance.
[embodiment 11] as described in Example 4, other conditions are identical, and only template uses MMT insteadC6B.Obtained production
Product are 0.64 g black powder, 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 for 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 are 0.79 V vs RHE, and electron transfer number 3.86, durability is good；Magnesium air battery
Performance is up to 56 mW/cm2.It is 148 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen analysis in the sulfuric acid solution of 0.5 mol/L
Take-off potential is 1.59 V vs RHE out, and limiting current density reaches 40 mA/cm2.Supercapacitor specific capacitance is 236 F/
G, be recycled 10000 times still holding capacitor value 95%.
[embodiment 12] as described in Example 4, other conditions are identical, only MMTC8B.Obtained product is 0.66 g
Black powder, test result show 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 ABPBI is added
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 battery performance is up to 75 mW/cm2.For its peak function of hydrogen-oxygen fuel cell
Rate is 206 mW/cm2.It is 1.57 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0. 5mol/L, and carrying current is close
Degree reaches 50 mA/cm2.Supercapacitor specific capacitance be 243 F/g, be recycled 10000 times still holding capacitor value 95%.
[embodiment 13] as described in Example 4, other conditions are identical, only MMTC14B.Obtained product is 0.70 g
Black powder, test result show that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, 0.1mol/
In L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential be 0.96 V vs RHE, electron transfer number 3.96,
Durability is good；Magnesium air battery performance is up to 95 mW/cm2.It is 365 mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5
It is 1.54 V vs RHE that take-off potential, which is precipitated, in the sulfuric acid solution oxygen of mol/L, and limiting current density reaches 80 mA/cm2.Super electricity
Container specific capacitance be 341 F/g, be recycled 10000 times still holding capacitor value 97%.
[embodiment 14] as described in Example 4, other conditions are identical, do not have to the method for vacuum aided, directly handle only
MMTC16BIt is added in the solution of ABPBI, is uniformly dispersed, is steamed near dry under stirring, done at 60 ~ 120 DEG C in vacuum oven
It is dry, it is finely ground, it is laid in porcelain boat bottom, under protection of argon gas 900 DEG C in high temperature furnace, is pyrolyzed 2 ~ 3h, it is cooling, finely ground, use hydrofluoric acid
Repeatedly washing, removes template agent removing, and obtaining product is 0.70 g black powder, and test result shows that its product remains as porous nitrogen
The carbon material of doping, in 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.79 V vs
RHE, electron transfer number 3.54, durability is good；Magnesium air battery 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, carrying current that take-off potential, which is precipitated, in the sulfuric acid solution oxygen of 0.5 mol/L
Density reaches 20 mA/cm2.Supercapacitor specific capacitance be 127 F/g, be recycled 10000 times still holding capacitor value 90%.
Claims (9)
1. a kind of method for preparing two-dimentional nitrogen-doped graphene in the microreactor of vertical direction confinement, it is characterised in that: hang down
Histogram is to use cationic surfactant C to the microreactor of confinement4~C16Alkyl dimethyl benzyl ammonium bromide modified montmorillonoid,
Abbreviation C-MMT, interlamellar spacing are adjusted by the alkyl chain length of cationic surfactant, and interlamellar spacing decision is filled
As poly- (2,5- benzimidazole) (ABPBI) of carbon source and nitrogen source how much, and then determine pyrolysis after obtain nitrogen-doped graphene
The number of plies；The method of the solution vacuum aided of soluble ABPBI is filled into the interlayer of C-MMT, and the interlamellar spacing of C-MMT exists
The mass ratio of 0.2~0.6nm, ABPBI and C-MMT are 2:1~1:3；Aromatic rings in the ABPBI molecule rule row in interlayer
Column are pyrolyzed 2~3h under inert gas protection, in high temperature furnace, remove C-MMT with hydrofluoric acid wash, prepare the two of high nitrogen-containing
Tie up nitrogen-doped graphene.
2. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
Method, it is characterised in that: the microreactor of vertical direction confinement is with cationic surfactant C4~C16Alkyl dimethyl benzyl
The modified montmorillonite of base ammonium bromide, abbreviation C-MMT, interlamellar spacing are adjusted by the alkyl chain length of cationic surfactant
Section, the interlamellar spacing of interlayer become hydrophobic between 0.2~0.6nm, interlayer, conveniently hydrophobic property macromolecule ABPBI molecule
Insertion.
3. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
Method, it is characterised in that: ABPBI macromolecular chain is made of the rigid benzimidazole of armaticity, and containing rich in nitrogen in molecule
The imidazole ring and Amino End Group of element；Polymer viscosity average molecular weigh can be dissolved in dimethyl acetamide between 1~30,000
(DMAc), any one in dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone is organic molten
Agent.
4. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
The mass ratio of method, ABPBI and C-MMT are 2:1~1:3；Concrete operations mode are as follows: weigh a certain amount of C-MMT in high temperature furnace
Interior 160~220 DEG C of heating 2h adsorbs water, gas or impurity, room temperature to be cooled to, the company of being transferred to remove in multilayer material interlayer
Have in the pressure vessel of vacuum pump, vacuumize 30~40 min, it is molten to inject a certain amount of ABPBI into pressure vessel with syringe
Liquid makes ABPBI solution impregnate C-MMT, continues to vacuumize, in the interlayer for forcing ABPBI molecule insertion C-MMT, to nothing in container
After liquid, continuation aforesaid operations run out up to ABPBI solution, drain；The C-MMT of sucking ABPBI solution, take out
60~120 DEG C of ageings in vacuum oven, drying, the sample for being cooled to room temperature takes out, finely ground, porcelain boat is put into, in high temperature furnace
Interior argon gas protection is lower to be pyrolyzed 2~3h, after furnace temperature is cooling, takes out sample, washes away C-MMT with hydrofluoric acid, be washed with deionized water
Acid, it is dry to get the two-dimentional nitrogen-doped graphene product for arriving black.
5. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
Method, pyrolysis temperature are 700~1100 DEG C.
6. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
The application of two-dimentional nitrogen-doped graphene prepared by method, it is characterised in that: the catalyst applied to catalytic oxidation-reduction reaction.
7. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
The application of two-dimentional nitrogen-doped graphene prepared by method, it is characterised in that: the catalysis for catalytic electrolysis water oxygen evolution reaction
Agent.
8. a kind of two-dimentional nitrogen-doped graphene of the preparation in the microreactor of vertical direction confinement according to claim 1
The application of two-dimentional nitrogen-doped graphene prepared by method, it is characterised in that: the electrode material for supercapacitor.
9. application according to claim 6, it is characterised in that: be applied to fuel cell, metal-air battery.
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| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| 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 |
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| CN105731424A (en) * | 2016-02-18 | 2016-07-06 | 山东科技大学 | Preparation method and application of nitrogen-doped nanoscale hollow carbon ball material |
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| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| 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 |
| CN104843692A (en) * | 2015-05-07 | 2015-08-19 | 常州大学 | Preparation method of two-dimensional sulfur nitrogen doped graphene |
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