CN106582816A - 用聚苯并咪唑制备多级孔道的三维氮掺杂石墨烯 - Google Patents
用聚苯并咪唑制备多级孔道的三维氮掺杂石墨烯 Download PDFInfo
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- CN106582816A CN106582816A CN201611235495.1A CN201611235495A CN106582816A CN 106582816 A CN106582816 A CN 106582816A CN 201611235495 A CN201611235495 A CN 201611235495A CN 106582816 A CN106582816 A CN 106582816A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 39
- 229920002480 polybenzimidazole Polymers 0.000 title claims abstract description 18
- 239000004693 Polybenzimidazole Substances 0.000 title abstract 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 54
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
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- 239000003054 catalyst Substances 0.000 claims abstract description 9
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- 239000011261 inert gas Substances 0.000 claims abstract description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
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- 229910052786 argon Inorganic materials 0.000 claims description 7
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- 239000000843 powder Substances 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
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 125000002883 imidazolyl group Chemical group 0.000 claims description 6
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 3
- -1 hydrochloric acid Alkene Chemical class 0.000 claims description 3
- 229920002521 macromolecule Polymers 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
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- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 abstract 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
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- 239000003990 capacitor Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
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- 229920000128 polypyrrole Polymers 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
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- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 5
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 229920000767 polyaniline Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 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
- 238000013019 agitation Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- ISMSDURUTAMCEA-UHFFFAOYSA-N [N].OP(O)(O)=O Chemical compound [N].OP(O)(O)=O ISMSDURUTAMCEA-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
本发明是一种制备多级孔道的三维氮掺杂石墨烯的方法。用聚苯并咪唑（PBI）中的mPBI或oPBI为碳源和氮源，用纳米碳酸钙作为模板剂，PBI溶解后与纳米模板剂混合，惰性气体保护下，热解，碳酸钙分解产生小孔，去模板后形成大孔，其大孔与小孔相互贯通的多级孔道的三维氮掺杂石墨烯，其贯通的多级孔道起到强化传质的效果。PBI选用可溶解聚物粘均分子量在3‑5万；碳酸钙粒径选用10～100nm颗粒；PBI：碳酸钙=2:1～1:4；热解温度为800~1100℃；稀盐酸去除模板剂。制备的多级孔道贯通的三维氮掺杂石墨烯用于燃料电池或金属空气电池阴极的氧还原催化剂，电解水阳极的氧析出催化剂，超级电容器电极材料等领域。
Description
技术领域
属于纳米材料制备领域，用于清洁能源领域的燃料电池、金属空气电池阴极催化剂，电解水催化剂，锂离子电池材料，超级电容器电极材料和电化学传感器等领域。。
背景技术
石墨烯特有的性质和优异物理化学性质引起人们的研究兴趣。二维石墨烯由于易发生层-层堆叠，得到石墨结构丧失石墨烯的特性。为此，人们开始三维石墨烯的研究(ChenK, et al. J Mater Chem（ 化学材料杂志）, 2012, 22: 20968)。三维石墨烯材料不仅具有石墨烯片层固有的理化性质，其三维多孔的微纳米结构还使其兼具比表面积大、电子传导性能好及强化传质等优良特性，使得三维石墨烯及其复合材料备受关注。三维石墨烯可应用于催化反应、燃料电池、传感器、超级电容器等领域表现出优异的性能(Cao X, et al.Energy Environ. Sci.(能源环境科学), 2014, 7:1850)。研究表明，碳材料掺杂后有很好的氧还原催化活性。在各类杂原子掺杂石墨烯中，氮掺杂石墨烯研究最多。二维氮掺杂石墨烯容易层层堆叠或聚集使活性位减少，而且由于缺少传质通道使其催化性能降低。而三维氮掺杂石墨烯可以使活性位暴露在反应的三相界面上，提高了反应效率，而且其多孔结构可提高反应物及产物的传质效率。三维氮掺杂石墨烯的制备方法有很多，如软模板法(DingW, et al. J Am Chem Soc (美国化学会志), 2015, 137(16): 5414)；硬模板法(Meng Y,et al. J Am Chem Soc(美国化学会志), 2014, 136(39): 13554)；用聚吡咯与氧化石墨烯热解制备3D氮掺杂石墨烯(Lin Z, et al. Nano Energy(纳米能源), 2013, 2(2):241)等等。
人们常用酚醛树脂、尿醛树脂、三聚氰胺树脂、聚苯胺和聚吡咯等热解制备碳材料，在热解制备多孔碳材料或石墨烯类无金属催化剂（Wu G, et al. Science(科学),2011, 332: 443)；Zhang L, et al. Sci Rep (科学报道), 2013, 3(3): 1408）。
作为含氮高分子材料，聚苯并咪唑（PBI）具有含氮量高的咪唑环结构。苯并咪唑环是芳香性的刚性环，在聚合物分子中容易出现堆积、聚集的现象，为了防止其堆积、聚集，可以在PBI分子中加入一些基团，使其改善其溶解性能和分子的柔顺性能。在PBI类高分子材料中，聚[2, 2’-(间苯基)-5, 5’-联苯并咪唑](mPBI)和聚[4, 4’-(二苯醚基)-5, 5’-联苯并咪唑]（oPBI）是常见的两种。
研究发现，PBI分子中咪唑环上的咪唑氮若与金属离子（如Cu、Mn、Fe、Ru、Ti、Mo和Os等）配位可以制备催化剂，用于催化有机化合物的氧化还原反应，其催化活性与稳定性能均较好(Cameron C G, et al. J Phys Chem B,（（美国）物理化学学报 B）2001, 105:8838)。多孔PBI树脂材料金属离子配位制备催化剂催化有机化合物的氧化还原反应（DArchivio, et al. Chem-A Eur J, (欧洲化学杂志)2000, 6(5): 794）其催化性能优良。PBI的合成方法可以分为5种：四胺与二腈、四胺与二酯、四胺与二酸、四胺与二酰胺、四胺与二醛，其中，芳香四胺与芳香二酸的反应最常用。mPBI和oPBI的结构式分别为:
mPBI的结构式 oPBI的结构式
本发明是利用芳香性的苯并咪唑作为提供碳和氮的原料，在惰性气体氩气保护下热解制备含氮的碳材料。通过改变原料与硬模板的比例、控制模板颗粒的大小来控制合成的含氮碳材料的孔径、孔隙率和石墨烯的层数等参数，最终得到理想的多层三维氮掺杂石墨烯。
与酚醛树脂、尿醛树脂等高分子材料相比，mPBI和oPBI的不同之处在于它含有芳香性的刚性的苯并咪唑环，而且咪唑环上的咪唑氮使其含氮量更加丰富。故高温热解mPBI和oPBI可以得到氮掺杂的碳材料，通过引入合适的模板或控制分子的芳香性环平面的排列方向，经热解后分别可以得到多层氮掺杂的石墨烯结构的材料。与聚苯胺和聚吡咯等材料制备氮掺杂石墨烯相比，mPBI和oPBI可溶解，易于涂饰在模板剂表面，而聚苯胺、聚吡咯等不溶解，无法与模板剂混合。
发明内容
本发明，发明了一种多级孔道贯通的三维氮掺杂石墨烯的制备方法。其碳源和氮源选用mPBI或oPBI，用纳米碳酸钙为模板剂，mPBI或oPBI分子中的芳香性的刚性的苯并咪唑分子可以规则地排列在模板剂纳米碳酸钙表面，在惰性气体保护下热解，在mPBI或oPBI热解生成氮掺杂碳材料的同时，模板剂碳酸钙也发生分解产生的二氧化碳排出会使模板剂之间，形成小孔的通道，除去纳米模板剂后可以形成多级孔道贯通（模板剂形成的孔和二氧化碳排出形成小孔贯通）三维氮掺杂石墨烯。要求 mPBI或oPBI是可溶性的，其分子中富含氮元素的咪唑环和端氨，苯并咪唑环是刚性的芳香性环，在热解时易形成氮掺杂石墨烯结构。其孔径、孔隙率、比表面积和氮掺杂石墨烯的层数等有mPBI或oPBI与纳米碳酸钙模板剂用量、模板剂的粒径等因素决定。小孔通道的形成靠纳米碳酸钙模板剂热解产生的二氧化碳的量决定。按照不同质量比混合、氩气保护下高温炉内热解2~3h，用稀盐酸去模板（此时变成氧化钙）即可得到的多级孔道贯通的三维氮掺杂石墨烯，其多级孔道贯通结构有利于电极的强化传质。该材料应用于燃料电池和金属空气电池阴极的氧还原催化剂，电解水氧析出催化剂及载体，超级电容器，电解、传感器材料等领域。
mPBI或oPBI与以上酚醛树脂、尿醛树脂和三聚氰胺树脂等高分子材料不同点是：mPBI或oPBI分子中苯并咪唑环属于芳香性的刚性环，易规则排列在模板剂表面，分子中咪唑环上含有咪唑氮，属于富氮的芳香型高分子聚合物。因此，其热解可以得到氮掺杂的多孔碳材料，如果mPBI或oPBI与模板剂的配比合适，控制分子的芳香环的平面按照一个方向排列，其热解可以得到氮掺杂的石墨烯结构。由于模板剂碳酸钙热解放出的二氧化碳会形成小的贯通的通道，因此，该方法可以制备多级孔道贯通的三维氮掺杂石墨烯结构材料。与聚苯胺、聚（邻苯二胺）、聚吡咯等高分子材料不同的是：mPBI或oPBI类高分子是可溶解在DMAc、DMSO等有机溶剂中，易与模板剂充分混合，不分相，由于其可溶性，其在制备3D氮掺杂石墨烯纳米材料时具有很好的操作性。然而，聚苯胺类、聚吡咯等高分子材料不可溶，无法与模板剂共混。纳米碳酸钙模板剂与纳米氧化镁、氧化铁和氢氧化铁模板剂相比不同处是碳酸钙在热解过程中碳酸钙会发生分解反应产生二氧化碳气体，该气体在排出时会形成贯通的小孔。该小孔与去除模板剂以后形成的纳米级的多孔三维氮掺杂石墨烯之间形成贯通的通道有利于该类材料用于电极反应过程中的强化传质。
mPBI或oPBI为液相法制备的粘均分子量在3万～5万之间的可以溶解在DMAc，DMF，DMSO，N-甲基吡咯烷酮等溶剂中。分子量太大，mPBI或oPBI的溶解性能变差；分子量太小其粘度太小，不能包覆模板剂。
纳米碳酸钙模板剂的粒径选用10~100nm，mPBI或oPBI与碳酸钙的质量比为2:1～1:4之间。三维氮掺杂的石墨烯的制备的方法为：首先制备聚合度适当的mPBI或oPBI，把mPBI或oPBI溶解在溶剂中形成溶液，向溶液中加入适量的粒径为10~100nm的纳米碳酸钙粉体做模板剂，搅拌使其充分混合均匀。在搅拌下，加热，慢慢地蒸出溶剂至近干，转入真空干燥箱中60~120℃下烘干。在研钵内研细，平铺在瓷舟底部，放入管式电炉内，在氩气保护下，在800～1100℃下，热解2~3h。待炉温冷却至室温，取出，用稀盐酸多次洗涤以去除模板纳米（此时应该为氧化钙），抽滤，用去离子水洗净，烘干得产品。
在本发明中，模板剂是纳米级的碳酸钙颗粒。能否制备出三维氮掺杂石墨烯，模板剂的粒径和加入量是关键：模板剂的粒径决定了制备的碳材料的孔径；模板剂的加入量决定了制备的石墨烯的层数、小孔的形成和性能，加入量太少，只能得到多孔碳材料，加入过多，得到的三维石墨烯层数太少，去除模板剂后，容易塌陷，只能得到破碎的石墨烯碎片。模板剂的颗粒度对加入模板剂的量有一定的影响，颗粒度小，其表面积大，需要的模板剂的量就少；反之，如果颗粒度大，需要的模板剂的量就多。贯通的小孔通道的形成与纳米碳酸钙的量和热解温度有关，热解温度在800℃以下，碳酸钙不分解，不能形成小孔贯通的通道。小孔的孔径与碳酸钙的量有关，碳酸钙产生的二氧化碳的量大，则可以形成的小孔的孔径就大些，如果产生的二氧化碳的量小，则形成的小孔就小。模板剂的用量为：mPBI或oPBI与模板剂的质量比为2:1～1:4；比例变化与模板的颗粒度有关。颗粒度从10~100nm。在惰性气体保护下热解，热解温度为：800～1100℃；洗涤用稀盐酸，多次洗涤后，用去离子水洗涤至中性即可。该类多级贯通的多孔材料对电极反应的传质有强化作用。
热解温度很重要，热解温度范围为800～1100℃。温度太低mPBI或oPBI不能热解，得到产品的导电性能差；碳酸钙不能分解无法得到小孔贯通的材料。热解温度到达最佳温度后，再升高热解温度其性能不变，如果氩气保护不充分，会使产品的催化性能变差，所以热解温度不宜过高。
多级孔道贯通的三维氮掺杂的石墨烯表征方法为：孔径、孔隙率、孔容和比表面积用氮气吸附仪（BET），产品的微观形貌分析用扫描电子显微镜（SEM）和投射电子显微镜（TEM），石墨烯层数可以通过高倍投射电子显微镜（HRTEM）和拉曼光谱来表征。产品的石墨化程度、石墨烯结构和层数可以用X-射线粉末衍射（XRD）、拉曼光谱来表征。产品的元素组成，价态可以用X-射线光电子能谱（XPS）进行了表征，用旋转圆盘电极（RDE）来测试产品的催化氧还原反应（ORR）性能、水电解氧析出反应（EOR），析氢反应（EHR）和产品的电容性能测试可以用循环伏安（CV）、线性伏安（LSV）、塔菲尔曲线和充放电性能来测试。产品作为催化剂的耐久性测试可以使用CV、LSV和计时电流曲线（i-t）。产品的催化性能最终需要组装金属空气电池、氢氧燃料电池、电解水的电解池、超级电容器和传感器来测试其性能。
具体实施方式
[实施例1] mPBI的制备：在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸(PPA) (100g)，氮气保护下160℃搅拌1h，以除去多余的水分及空气。将DABz (4g, 18.7mmol) 以及间苯二甲酸 (3.1g, 18.7 mmol) 混合均匀，慢慢加入到三口烧瓶中。控制氮气流速，防止DABz被氧化，同时将反应温度提升到200℃并继续保温、搅拌反应5-8h。随着反应时间的增加，聚合体系逐渐变得粘稠。待粘度合适时停止反应，反应混合液慢慢转移到大量去离子水中抽丝，洗净、烘干，粉碎，去离子水多次洗涤以除去多聚磷酸和未反应反应物，即得到mPBI，用乌氏粘度计测定mPBI的分子量。
[实施例2] oPBI的合成法：在装有电动搅拌和氮气保护的三口烧瓶中加入多聚磷酸 (PPA) (100g)，氮气保护下160℃搅拌2h以排除空气及水分。将DABz (4g, 18.7mmol) 以及4,4’-二苯醚二甲酸(4.83g，18.7 mmol) 混合均匀，慢慢加入到三口烧瓶中。控制氮气流速，防止DABz被氧化，同时将反应温度提升到200℃并继续保温、搅拌反应5~8h。随着反应时间的增加，聚合体系逐渐变得粘稠。待粘度合适时停止反应，反应混合液慢慢转移到大量去离子水中抽丝，洗净、烘干，粉碎，去离子水多次洗涤以除去多聚磷酸和未反应反应物，即得到oPBI，用乌氏粘度计测定oPBI的分子量。
[实施例3] 用粒径30nm的碳酸钙颗粒为模板剂与mPBI混合，以mPBI与纳米级的碳酸钙模板剂质量比为1:1为例：
在250mL的烧杯中，加入1g的mPBI（粘均分子量3~5万）和20mL DMAc，加热、搅拌使其溶解，在搅拌下慢慢加入1g粒径为30nm的碳酸钙使其分散均匀。得到的粘稠状液体在搅拌下加热浓缩至近干，在真空干燥箱内100℃下干燥，固体在研钵内研细，转移到瓷舟内，在氩气保护下，在高温电炉内900℃下热解，保温2-3h，待炉温降至室温，取出，研细，得到黑色粉末状固体，转移到250mL锥形瓶中，加入70mL的3mol/L盐酸，加热、搅拌8h，抽滤，用稀盐酸洗涤三次、水洗至中性，干燥得到黑色粉末状固体产品0.68g。BET测试表明，其孔径分布为30nm和2~4nm小孔，1431 m2 g-1，SEM测试表明，得到的产品为多孔泡沫状碳材料，TEM和HRTEM分析表明，产品为三维石墨烯结构碳材料，孔径为30nm，小孔2~4nm，孔道贯通。石墨烯彀回表明为2~4层石墨烯。XRD和拉曼光谱测试表明，产品为2~4层的石墨烯结构；XPS分析表明，产品氮含量为7.2%，且氮为吡啶型氮和吡咯型氮。说明，产品是多级孔道贯通的氮掺杂的三维石墨烯结构的材料。其0.1mol/LKOH溶液中，催化氧还原性能，起始氧还原电位为0.96V vsRHE，电子转移数为3.97，耐久性良好；镁空气电池性能达97mW/cm2。用于氢氧燃料电池其峰功率为612 mW/cm2，0.5mol/L的硫酸溶液中氧析出起始电位为1.54 vs RHE， 极限电流密度达到115mA/cm2。超级电容器比电容为461F g-1 ，可循环10000 次仍保持电容值的98%。
[实施例4] 按实施例3的方法，其它条件相同，只是mPBI：碳酸钙=2:1。得到的产品为0.72g黑色粉末，BET测试表明，其孔径分布为30nm和2~4nm小孔，823 m2 g-1，SEM测试表明，得到的产品为多孔泡沫状碳材料，TEM和HRTEM分析表明，产品为三维石墨烯结构碳材料，孔径为30nm，小孔2~4nm，孔道贯通。石墨烯彀回表明为7~8层石墨烯。XRD和拉曼光谱测试表明，产品为7~8层的石墨烯结构；XPS分析表明，产品氮含量为7.4%，且氮为吡啶型氮和吡咯型氮。说明，产品是氮掺杂的三维石墨烯结构的材料。测试结果表明，其产品仍然为的多级孔道贯通的多孔三维氮掺杂石墨烯结构的材料。其0.1mol/L KOH溶液中，催化氧还原性能，氧气起始还原电位为0.85V vs RHE，电子转移数为3.86，耐久性良好；镁空气电池性能达77mW/cm2。用于氢氧燃料电池其峰功率为358mW/cm2，0.5mol/L的硫酸溶液中氧析出起始电位为1.57 vs RHE， 极限电流密度达到60mA/cm2。超级电容器比电容为347F g-1 ，可循环10000 次仍保持电容值的94%。
[实施例5] 按实施例3的方法，其它条件相同，只是改变热解温度改为1100℃，其他条件同上，只是改变热解温度。得到的产品为0.65g黑色粉末，测试结果表明，其产品仍然为2~4层的多孔三维氮掺杂石墨烯结构的材料，其电化学性能同实施例3。
[实施例6] 按实施例3的方法，其他条件相同，只是mPBI：碳酸钙=1：2，同样得到黑色的固体粉末。BET测试表明，其孔径分布范围30~60 nm，小孔2~6 nm，但是其比表面积则降为1233 m2 g-1，其SEM和TEM测试表明，其内部为多级孔结构的碳材料，表面为多层石墨烯结构，XRD和拉曼数据表明，其石墨烯的层数6~8层。XPS数据与实施例3的产品类似。其0.1mol/LKOH溶液中，催化氧还原性能，氧气起始还原电位为0.87V vs RHE，电子转移数为3.84，耐久性良好；镁空气电池性能达66mW/cm2。用于氢氧燃料电池其峰功率为269mW/cm2，0.5mol/L的硫酸溶液中氧析出起始电位为1.57V vs RHE， 极限电流密度达到40mA/cm2。超级电容器比电容为348F g-1，可循环10000 次仍保持电容值的94%。
[实施例7] 按实施例3的方法，其它条件相同，只是用粒径为70nm的碳酸钙颗粒做模板剂，这时由于模板剂的粒径变大，其表面积减小，mPBI的用量减少，则mPBI与模板剂的质量比改为为1:3，得到的产品同实施例3，只是其孔径分布在70nm，小孔3~6 nm，比表面积为1016 m2 g-1，为2~4层的三维氮掺杂石墨烯材料。其0.1mol/LKOH溶液中，催化氧还原起始电位为0.91V vs RHE，电子转移数为3.93，耐久性良好；镁空气电池性能达94 mW/cm2。用于氢氧燃料电池其峰功率为362mW/cm2，0.5mol/L的硫酸溶液中氧析出起始电位为1.58V vsRHE， 极限电流密度达到60mA/cm2。超级电容器比电容为336F g-1，可循环10000 次仍保持电容值的94%。
[实施例8] 按实施例3的方法，其它条件相同，只是用粒径为100nm的碳酸钙颗粒做模板剂，这时由于模板剂的粒径增大，其表面积减小，mPBI的用量减少，则mPBI与模板剂的质量比改为为1:4，得到的产品同实施例3，只是其孔径分布在100 nm，小孔3~6 nm，比表面积为764 m2 g-1，为3~5层的多级孔道的三维氮掺杂石墨烯材料，催化氧还原起始电位为0.91V vs RHE，电子转移数为3.87，耐久性良好；镁空气电池性能达88 mW/cm2。用于氢氧燃料电池其峰功率为356 mW/cm2，0.5 mol/L的硫酸溶液中氧析出起始电位为1.59V vs RHE，极限的里面的达到57 mA/cm2 。超级电容器比电容为278F g-1，可循环10000 次仍保持电容值的93%。
[实施例9]用用oPBI为碳源和氮源（粘均分子量在3-5万），其它实验条件同实施例3。粒径为30纳米的碳酸钙为模板剂。oPBI与模板剂的质量比为1:1。其结果与实施例3类似。孔径为30nm，小孔为3-4nm，1334.1 m2 g-1，为2~4层石墨烯。氮含量为6.6%，且氮为吡啶型氮和吡咯型氮。说明，产品是氮掺杂的三维石墨烯结构的材料。其0.1mol/LKOH下催化氧还原性能，氧气起始还原电位为0.96V vs RHE，电子转移数为3.95，耐久性良好；镁空气电池性能达87mW/cm2。用于氢氧燃料电池其峰功率为368mW/cm2，0.5mol/L的硫酸溶液中氧析出起始电位为1.57V vs RHE， 极限电流密度达到66mA/cm2。超级电容器比电容为457F g-1，可循环10000 次仍保持电容值的96%。用oPBI为碳源和氮源，用其它粒径的模板剂其结果与上述实施例类似。
Claims (6)
1.一种多级孔道贯通的三维氮掺杂石墨烯的制备方法，其特征在于：其碳源和氮源选用聚苯并咪唑（PBI）中的mPBI或oPBI，该类高分子化合物分子内有芳香性的刚性的苯并咪唑环可以规则地排列在模板剂纳米碳酸钙表面，在惰性气体保护下热解，在热解过程中PBI得到氮掺杂碳材料，碳酸钙热解产生的二氧化碳会在模板剂之间形成小的通孔，去除纳米模板剂后，得到多级孔道贯通的三维氮掺杂石墨烯材料； mPBI或oPBI是可溶性的，其分子中富含氮元素的咪唑环和端氨，且其苯并咪唑环是刚性的芳香性环，在热解时易形成氮掺杂石墨烯结构； mPBI或oPBI溶液与不同粒径纳米碳酸钙模板剂按照不同质量比混合、氩气保护下高温炉内热解2~3h，用稀盐酸去模板即可得到的多级孔道贯通的三维氮掺杂石墨烯，其多级孔道结构有利于电极的强化传质。
2.根据权利要求1所述的mPBI或oPBI，其特征在于：高分子链是由芳香性的刚性苯并咪唑组成，且分子中含有富含氮元素的咪唑环和端氨基；聚合物粘均分子量在3～5万之间，可以溶解在二甲基乙酰胺（DMAc）、二甲基甲酰胺（DMF）、二甲基亚砜（DMSO）和N-甲基吡咯烷酮等有机溶剂。
3.根据权利要求1所述的模板为纳米碳酸钙粉体，其特征在于，粒径在10～100nm。
4.根据权利要求1所述的mPBI或oPBI与模板碳酸钙的质量比为2:1～1:4；混合方式为：mPBI或oPBI溶液与纳米碳酸钙颗粒混合，搅拌混合均匀后，搅拌下加热蒸出溶剂至近干，真空干燥，研细，在高温炉内氩气保护下热解，用稀盐酸酸洗涤以去除模板，即可得到多级孔道贯通的三维氮掺杂石墨烯。
5.根据权利要求1所述的热解温度为800～1100℃。
6.根据权利要求1所述的多级孔道贯通的三维氮掺杂石墨烯，应用于催化氧还原反应的催化剂，用在金属空气电池、燃料电池；也可用于催化电解水氧析出反应的催化剂；还可用于超级电容器的电极材料。
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