CN111744522A - Universal preparation and application of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on sol-gel method - Google Patents
Universal preparation and application of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on sol-gel method Download PDFInfo
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- CN111744522A CN111744522A CN202010629085.5A CN202010629085A CN111744522A CN 111744522 A CN111744522 A CN 111744522A CN 202010629085 A CN202010629085 A CN 202010629085A CN 111744522 A CN111744522 A CN 111744522A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 144
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 72
- 239000004964 aerogel Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000003980 solgel method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000017 hydrogel Substances 0.000 claims abstract description 28
- -1 nitrogenous macrocyclic compound Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910015183 FeNx Inorganic materials 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 229910016547 CuNx Inorganic materials 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 229910018874 CoNx Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000000197 pyrolysis Methods 0.000 claims abstract description 6
- 239000012670 alkaline solution Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 229920000768 polyamine Polymers 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
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- 239000007788 liquid Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical group ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 4
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 claims description 2
- CMPNPRUFRJFQIB-UHFFFAOYSA-N [N].[Cu] Chemical compound [N].[Cu] CMPNPRUFRJFQIB-UHFFFAOYSA-N 0.000 claims description 2
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical group [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 claims description 2
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000004299 exfoliation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- 238000012360 testing method Methods 0.000 description 11
- 125000004429 atom Chemical group 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
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- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
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- 230000004931 aggregating effect Effects 0.000 description 1
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- 239000006255 coating slurry Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/391—Physical properties of the active metal ingredient
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- 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
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- 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
- H01M4/9041—Metals or alloys
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- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses universal preparation and application of a nitrogen-rich graphene aerogel load monatomic cluster catalyst based on a sol-gel method. The preparation of the catalyst comprises the following steps: 1) reacting cyanamideThe polymer powder is pyrolyzed in an inert gas atmosphere to obtain g-C3N4A yellow powder; 2) carrying out multi-step oxidation stripping treatment on graphite powder to prepare graphene oxide GO; 3) GO, g-C3N4And a suspension formed by a macrocyclic organic metal compound or a nitrogenous macrocyclic compound is subjected to a hydrothermal reaction to obtain hydrogel; 4) and freezing and drying the hydrogel, and then carrying out high-temperature pyrolysis in an inert atmosphere to obtain the nitrogen-rich graphene aerogel supported monatomic cluster catalyst. The nitrogen-enriched graphene aerogel loaded one or more than one atomic cluster catalyst of FeNx, CoNx and CuNx obtained by the invention has excellent catalytic activity and stability on ORR or OER in an alkaline solution, and has good application prospect in fuel cells, metal-air cells and water electrolysis. The method has the advantages of simple and safe operation process, low cost, controllable preparation, large-scale synthesis and the like, and is suitable for industrial production and large-scale application.
Description
Technical Field
The invention belongs to the technical field of monatomic cluster catalyst synthesis, and particularly relates to a universal preparation method of a nitrogen-rich graphene aerogel supported monatomic cluster catalyst, the nitrogen-rich graphene aerogel supported monatomic cluster catalyst and application.
Background
The demand of human beings on energy is gradually increased, non-renewable energy sources such as petroleum are gradually exhausted, and the seeking of petroleum substitutes is a necessary requirement for realizing low-carbon economy and reducing environmental pollution. In recent years, with the development of technologies, renewable energy sources such as wind energy, hydroelectric energy, solar energy and the like are increasingly utilized. The key to the sustainable development and application of clean energy is the search for safe, reliable and efficient storage methods and efficient utilization technologies for renewable and sustainable energy. Currently, renewable energy conversion and storage systems such as fuel cells, metal-air batteries, and water electrolysis devices have thus received extensive attention and development. The retarded kinetics of the oxygen reduction (ORR) and Oxidation (OER) processes remain the biggest obstacles in the development and application of fuel cell, metal-air cell and electrolytic water technologies. The search for efficient, stable, low cost ORR and OER catalysts remains a vital task in developing energy conversion and storage technologies for fuel cells, metal-air cells, and electrolysis of water.
The method is widely researched and verified by scientific researchers: among the non-noble metal catalysts, metal nitrides (MNx) are the main active centers that generally exhibit high activity for ORR and OER processes. Extensive researchers are currently developing high performance ORR and OER catalysts by designing reasonable nanostructures and regulating sizes, mainly based on the inexpensive price of non-noble metals, abundant earth reserve resources.
Atomic scale catalysts have attracted considerable attention from researchers since 2011 billows the successful synthesis of iron-based single atom active site catalysts and the introduction of the concept of "single atom catalysts". On one hand, the atomic-scale catalyst can greatly improve the number of active sites and realize high atom utilization rate due to the completely exposed atoms, and on the other hand, the low-coordination unsaturated state of the atomic-scale catalyst and the enhanced interaction of a metal carrier can obviously improve the intrinsic activity of the active sites. Thus, scientists have recently vigorously conducted studies to regulate the activity and utilization of catalysts based on monatomic catalysts.
However, compared to monatomic catalysts, cluster catalysts are less of a scientific concern. The atomic cluster is formed by aggregating a small number of atoms, is larger than a single atom in size, and even reaches the nanometer level when the number of the aggregated atoms reaches a certain number. Clusters containing only a small number of atoms exhibit exceptional and unexpected performance due to high surface atomic ratios, nano-sized characteristics that are different from bulk catalysts, low catalyst usage and effective catalyst utilization. Reported research work has shown that gold atom cluster catalysts, platinum atom cluster catalysts, Fe cluster catalysts (C/TP-Fe700), and conix single cluster (C/P/2Co600), etc., all exhibit excellent catalytic activity in specific environments. However, the preparation of highly dispersed, highly active nitrogen-rich graphene aerogel supported MNx monatomic cluster catalysts by a simple and clean method suitable for industrial production and large-scale application without the use of surfactants remains a significant challenge.
Disclosure of Invention
The invention provides universal preparation and application of a nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on a sol-gel method, the preparation method can be generally suitable for synthesis of various nitrogen-rich graphene aerogel supported monatomic cluster catalysts, and the preparation method has the advantages of simple and safe operation process, low cost, controllable preparation, large-scale synthesis and the like, and is suitable for industrial production and large-scale application. The nitrogen-rich graphene aerogel-loaded one or more than one atomic cluster catalyst of FeNx, CoNx and CuNx prepared by the method has excellent catalytic activity and stability on ORR or OER in an alkaline solution, and has good application prospects in fuel cells \ metal-air cells and water electrolysis.
The invention is mainly realized by adopting the following technical scheme:
1. a general preparation method of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on a sol-gel method is characterized by comprising the steps of preparing graphene and graphitized carbon nitride (g-C)3N4) Preparing nitrogen-enriched graphene aerogel serving as a carrier of the metal monatomic cluster;
2. a sol-gel method-based universal preparation method of nitrogen-rich graphene aerogel supported monatomic cluster catalyst is disclosed, wherein a catalyst active center is uniformly supported on a nitrogen-rich graphene aerogel carrier in a monatomic cluster form;
3. a universal preparation method of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on a sol-gel method comprises the following steps:
1)g-C3N4the preparation of (1): decomposing cyanamide polymer powder at high temperature in inert gas atmosphere, and cooling to obtain g-C3N4A yellow powder;
2) preparation of graphene oxide GO: carrying out multi-step oxidation stripping treatment on graphite powder, and carrying out acid pickling, water washing and drying to obtain graphene oxide GO;
3) preparing nitrogen-enriched graphene hydrogel: ultrasonically dispersing the prepared graphene oxide in ultrapure water uniformly, adding a macrocyclic organic metal source precursor or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and a metal inorganic salt precursor and the prepared g-C3N4Ultrasonic, based on GO, g-C3N4And self-assembling and coordinating macrocyclic organic metal compound or nitrogenous macrocyclic compound to form uniform suspension, and then transferring the suspension into a high-temperature reaction kettle to perform hydrothermal reaction for a certain time to obtain nitrogen-rich graphene hydrogel;
4) preparing a nitrogen-enriched graphene aerogel supported monatomic cluster catalyst: and freeze-drying the hydrogel, and then performing high-temperature pyrolysis in an inert atmosphere to obtain the nitrogen-rich graphene aerogel supported monatomic cluster catalyst.
Preferably, in the step 1), the cyanamide polymer is dicyandiamide or melamine.
Preferably, in step 1), the inert gas is nitrogen or argon or helium.
Preferably, in the step 1), the decomposition temperature is 300-900 ℃, and the decomposition time is 40 min-6 h.
Preferably, in the step 2), the graphene oxide GO is prepared by a multi-step oxidation stripping method of graphite powder. The method comprises the following steps:
a) 1-20 mL of concentrated H2SO40.3 to 5g of K2S2O8And 0.3 to 5g of P2O5And (3) fully mixing in an ice bath, adding 1-5 g of graphite powder into the mixed solution, and raising the temperature to 50-90 ℃ in an oil bath for pre-oxidation for 0.5-5 h. Then standing and cooling to room temperature, diluting with 0.3-1L of deionized water, filtering and collecting a solid product, continuously washing with deionized water to be neutral, and standing overnight and naturally drying for later use;
b) adding the solid product prepared in the step a) into concentrated H in 30-150 mL ice bath2SO4With concentrated H3PO4The mixed concentrated acid (volume ratio is 4-9: 1) is slowly added with 5-20 g of KMnO4Further oxidizing and keeping the temperature below 20 ℃ for 0.2-1 h, then heating to 30-45 ℃ for reaction for 1-6 h, diluting with 250-1000 mL of deionized water after reaction, and cooling to room temperature;
c) treating the unreacted KMnO in the solution in the step b) with 10-30 mL of 30 wt% H2O24Uniformly stirring until the reaction is finished, washing with a dilute HCl solution (1L), and then washing with deionized water until the reaction is neutral; and finally, carrying out vacuum drying to obtain the graphene oxide GO.
Preferably, in the step 3), the macrocyclic organic metal precursor is iron phthalocyanine, cobalt phthalocyanine or copper phthalocyanine; iron porphyrin, cobalt porphyrin or iron porphyrin; or a mixture of two thereof; or macrocyclic compounds containing nitrogen (aza crown ethers and macrocyclic polyamines) are mixed with iron nitrate, cobalt nitrate, copper nitrate or chloride, cobalt chloride, copper chloride or iron sulfate, cobalt sulfate, copper sulfate.
When the metal precursor is iron phthalocyanine or iron porphyrin or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and ferric nitrate or ferric chloride or ferric sulfate, the obtained catalyst material is a nitrogen-rich graphene aerogel supported iron-nitrogen cluster catalyst;
when the metal precursor is cobalt phthalocyanine or cobalt porphyrin or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and cobalt nitrate or cobalt ferric chloride or cobalt sulfate, the obtained catalyst material is a nitrogen-rich graphene aerogel supported cobalt-nitrogen atom cluster catalyst;
when the metal precursor is copper phthalocyanine or copper porphyrin or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and copper nitrate or copper chloride or copper sulfate, the obtained catalyst material is a nitrogen-rich graphene aerogel supported copper nitrogen cluster catalyst;
when the metal precursor is an organic metal precursor mixture or a mixture of aza-crown ether, macrocyclic polyamine and metal inorganic salt, the obtained catalyst material is an atomic cluster catalyst of nitrogen-rich graphene aerogel loaded with mixed metal nitride;
preferably, in the step 3), the preparation of the nitrogen-enriched graphene hydrogel is performed according to the following process:
adding 40 mg-0.5 g of GO prepared in the step 2) into 40-200 mL of ultrapure water for ultrasonic dispersion to obtain a yellow GO dispersion liquid; subsequently, an organometallic precursor or a nitrogen-containing macrocyclic compound (azacrown ether and macrocyclic polyamine) is combined with the metal inorganic salt precursor mixture and g-C3N4According to different GO: g-C3N4Adding metal precursors into GO dispersion liquid according to the mass ratio of 4:8:1, 3:6:1, 2:4:1, 1:2:1, 2:3:1 and 2:4.5:1, and carrying out ultrasonic treatment for 1-6 hours until the color of the solution changes from brown yellow to light green and finally to dark green. And then transferring the suspension into a proper high-temperature reaction kettle, carrying out hydrothermal treatment at 120-200 ℃ for 6-30 hours to obtain the nitrogen-rich graphene hydrogel.
Preferably, in the step 4), the hydrogel prepared in the step 3) is subjected to freeze drying for 24 hours; and then performing high-temperature pyrolysis for 1-4 h in nitrogen or argon or helium at the temperature of 500-950 ℃ to obtain the nitrogen-rich graphene aerogel supported monatomic cluster catalyst.
4. The nitrogen-rich graphene aerogel supported monatomic cluster catalyst is prepared by the method. The nitrogen-enriched graphene aerogel loads a monatomic cluster catalyst with one or more than one active sites of monatomic cluster catalysts FeNx, CoNx and CuNx.
5. The nitrogen-enriched graphene aerogel supported FeNx, CoNx and CuNx monatomic cluster active site catalyst is used for chemical reaction in an electrocatalytic alkaline solution and is used as an electrocatalyst.
Preferably, the nitrogen-enriched graphene aerogel supported FeNx monatomic cluster active site catalyst is used for catalyzing the oxygen reduction (ORR) reaction of a fuel cell or a metal-air cell under alkaline conditions; the nitrogen-enriched graphene aerogel supported CoNx and CuNx single-atom cluster active site catalyst and one or more than one type of supported FeNx, CoNx and CuNx active sites are used for catalyzing oxygen reduction (ORR) reaction of a fuel cell or a metal-air cell and OER reaction of electrolyzed water under alkaline conditions.
Description of the drawings
FIG. 1 photograph of FeNx monatomic cluster nitrogen-rich graphene aerogel
FIG. 2 is an SEM photograph (a), a TEM photograph (b) and an HRTEM photograph (c) of Fenx-CN/g-GEL
FIG. 3 SEM and TEM images of CuNx-CN/g-GEL
Detailed Description
The following examples are given to illustrate the present invention in more detail, but do not limit the scope of the claims of the present invention.
Example 1
(1) Preparation of g-C3N4: putting 3g of melamine powder into a porcelain boat, thermally decomposing for 2h in Ar gas at 500 ℃, cooling, and collecting to obtain g-C3N4Yellow powder.
(2) Preparing GO:
a) 8mL of concentrated H2SO41.0g of K2S2O8And 1.0g of P2O5And (3) fully mixing in an ice bath, adding 3g of graphite powder into the mixed solution, heating in an oil bath to 80 ℃ for pre-oxidation, and keeping for 2.5 hours. Then standing and cooling to roomDiluting with 0.5L of deionized water, filtering and collecting a solid product, continuously washing with deionized water to be neutral, and naturally drying overnight for later use;
b) adding the solid product prepared in step a) to concentrated H in a 120mL ice bath2SO4With concentrated H3PO4To the mixed concentrated acid of (5: 1 by volume), followed by slow addition of 12g KMnO4Further oxidizing and keeping the temperature below 20 ℃ for 1h, then heating to 30-45 ℃ for reaction for 2h, diluting with 1000mL of deionized water after the reaction, and cooling to room temperature;
c) with 20mL of 30 wt% H2O2Processing unreacted KMnO in the solution of step b)4Uniformly stirring until the reaction is finished, washing with 12% diluted HCl solution (1L), and then washing with deionized water until the reaction is neutral; and finally, carrying out vacuum drying to obtain the graphene oxide GO.
(3) Preparing nitrogen-rich graphene hydrogel: adding 60mg of GO into 60mL of ultrapure water to obtain 1mg/mL of yellow GO dispersion liquid; then, 30mg of FePc and 120mg of g-C were added3N4And simultaneously adding the GO into the GO dispersion liquid, and carrying out ultrasonic treatment for 4 hours until the color of the solution changes from brown yellow to light green and then to dark green. Then, transferring the suspension into a 100mL high-temperature reaction kettle, carrying out hydrothermal treatment at 160 ℃ for 12 hours to obtain hydrogel;
(4) preparing a nitrogen-enriched graphene aerogel supported FeNx monatomic cluster catalyst: and freeze-drying the prepared hydrogel for 24 hours, and then pyrolyzing the hydrogel for 2 hours in Ar-atmosphere at 600 ℃ to obtain the nitrogen-rich graphene aerogel supported FeNx monatomic cluster catalyst FeNx-CN/g-GEL. FIG. 1 is a photograph of a FeNx monatomic cluster nitrogen-rich graphene aerogel (FeNx-CN/g-GEL) prepared by the method. FIG. 2 shows SEM images (a), TEM (b) and HRTEM images (c) of FeNx-CN/g-GEL, respectively.
Example 2
(1) Preparation of g-C3N4: placing 5g of melamine powder in a porcelain boat, thermally decomposing for 4h at 550 ℃ in Ar gas, cooling, and collecting to obtain g-C3N4Yellow powder.
(2) Preparing GO:
a) 10mL of concentrated H2SO42.0g of K2S2O8And 2.0g of P2O5And (3) fully mixing in an ice bath, adding 3g of graphite powder into the mixed solution, heating in an oil bath to 80 ℃ for pre-oxidation, and keeping for 3 hours. Then standing and cooling to room temperature, diluting with 0.5L of deionized water, filtering and collecting a solid product, continuously washing with deionized water to be neutral, and standing overnight and naturally drying for later use;
b) adding the solid product prepared in step a) to concentrated H in a 120mL ice bath2SO4With concentrated H3PO4To the mixed concentrated acid of (6: 1 by volume), followed by slow addition of 12g KMnO4Further oxidizing and keeping the temperature below 20 ℃ for 1h, then heating to 30-45 ℃ for reaction for 2h, diluting with 1000mL of deionized water after the reaction, and cooling to room temperature;
c) with 20mL of 30 wt% H2O2Processing unreacted KMnO in the solution of step b)4Uniformly stirring until the reaction is finished, washing with 12% diluted HCl solution (1L), and then washing with deionized water until the reaction is neutral; and finally, carrying out vacuum drying to obtain the graphene oxide GO.
(3) Preparing nitrogen-rich graphene hydrogel: adding 60mg of GO into 60mL of ultrapure water to obtain 1mg/mL of yellow GO dispersion liquid; then, 30mg of CuPc and 120mg of g-C were added3N4And simultaneously adding the GO into the GO dispersion liquid, and carrying out ultrasonic treatment for 4 hours until the color of the solution changes from brown yellow to light green and then to dark green. Then, transferring the suspension into a 100mL high-temperature reaction kettle, carrying out hydrothermal treatment at 160 ℃ for 18 hours to obtain hydrogel;
(4) preparing a nitrogen-enriched graphene aerogel supported CuNx monatomic cluster catalyst: and freeze-drying the prepared hydrogel for 24 hours, and then pyrolyzing the hydrogel for 2 hours in Ar-atmosphere at 600 ℃ to obtain the nitrogen-rich graphene aerogel supported CuNx monatomic cluster catalyst CuNx-CN/g-GEL. FIG. 3 is a TEM image (a) and an HRTEM image (b) of CuNx-CN/g-GEL prepared by the present invention, respectively.
Comparative example 1:
adding 60mg of GO into 60mL of ultrapure water to obtain 1mg/mL of yellow GO dispersion liquid; then, 120mg of g-C3N4Adding into GO dispersion, and performing ultrasonic treatment for 4 h. Next, the suspension was transferred to a height of 100mLIn a warm reaction kettle, performing hydrothermal treatment at 160 ℃ for 24 hours to obtain hydrogel; freeze-drying the hydrogel for 24 hours, and then pyrolyzing the hydrogel for 2 hours in an Ar-atmosphere at 650 ℃ to obtain nitrogen-enriched graphene aerogel CN/g-GEL;
comparative example 2:
adding 60mg of GO into 60mL of ultrapure water to obtain 1mg/mL of yellow GO dispersion liquid; then, 30mg of FePc was added to the GO dispersion and sonicated for 4 h. Then, transferring the suspension into a 100mL high-temperature reaction kettle, carrying out hydrothermal treatment at 160 ℃ for 24 hours to obtain hydrogel; and (3) freeze-drying the hydrogel for 24 hours, and then pyrolyzing the hydrogel for 2 hours in an Ar-atmosphere at 650 ℃ to obtain iron phthalocyanine and graphene aerogel FeNx/g-GEL.
Example 3
The nitrogen-enriched graphene aerogel prepared in example 1 loaded with the FeNx monatomic cluster catalyst FeNx-CN/g-GEL and a comparative example are subjected to an ORR (organic solvent resistance) catalytic performance test. And (3) testing conditions are as follows: weighing 3mg of catalyst, placing the catalyst in a 2mL small test tube, adding 975 microliters of isopropanol and 25 microliters of Nafion solution into the upper test tube, and carrying out ultrasonic treatment for 30 min; 15 microliters of the slurry was dropped onto the electrode surface and then tested for ORR performance in oxygen saturated 0.1M KOH with an LSV test sweep rate of 10mV/s and a rotational speed of 1600 rm. E of FeNx-CN/g-GELonset1.0V, very close to commercial Pt/C (1.04V), half-wave potential (E)1/2) Up to 0.90V, 65mV higher than commercial Pt/C catalyst and also significantly higher than the half-wave potential (CN/g-GEL E) of the comparative example1/2E at 0.756V, FeNx/g-GEL1/20.864V).
Example 4
The nitrogen-rich graphene aerogel prepared in the example 2 loaded with the CuNx monatomic cluster catalyst CuNx-CN/g-GEL is subjected to ORR catalytic performance test and zinc-air battery assembly application.
ORR catalytic performance test conditions: weighing 3mg of catalyst, placing the catalyst in a 2mL small test tube, adding 975 microliters of isopropanol and 25 microliters of Nafion solution into the upper test tube, and carrying out ultrasonic treatment for 30 min; 10 microliter of the slurry was dropped onto the electrode surface and then tested for ORR performance in oxygen saturated 0.1M KOH with an LSV test sweep rate of 10mV/s and a rotational speed of 1600 rm. Half-wave potential (E) of CuNx-CN/g-GEL1/2) Reaching 0.774V, close to commercial Pt/C catalysts.
Assembling a zinc-air battery, namely taking foamed nickel as a positive electrode, weighing 4 mg of the catalyst prepared in the example 2, grinding and mixing 12 mg of acetylene black, adding a proper amount of ethanol and 25 mL of polytetrafluoroethylene solution, uniformly stirring, coating slurry on 2cm × 2cm foamed nickel, tabletting by using a roller press, treating and drying the treated foamed nickel for later use to obtain a positive electrode material with the load of 1mg/mL, taking a zinc sheet as a negative electrode, selecting a zinc sheet with the thickness of 1 mm, polishing the zinc sheet, and preparing 6M +0.2M Zn (Ac)2The mixed solution is used as an electrolyte for standby, and zinc acetate ensures the reversible reaction of zinc in the redox reaction. The discharge/charge performance and cycle performance were measured on a test apparatus model LAND-CT3001A, and throughout the test, the anode was exposed to air and oxygen was continuously supplied to the anode. The charge and discharge tests are carried out at the current density of 10mA cm2And (5) testing under the condition.
The open circuit voltage of the assembled zinc-air battery reaches 1.372V, and is higher than RuO reported in the literature2+ Pt/C as the cathode open circuit voltage (1.35V). Two groups of zinc-air batteries which are based on CuNx-CN/g-GEL as a cathode catalyst are connected in series, so that the light-emitting diodes with the voltage of 2V-2.5V can be lightened, and the brightness can be kept unchanged for a period of time.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A universal preparation method of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on a sol-gel method is characterized in that graphene and graphitized carbon nitride (g-C) are used3N4) Preparing nitrogen-enriched graphene aerogel serving as a carrier of the metal monatomic cluster;
2. a sol-gel method-based universal preparation method of nitrogen-rich graphene aerogel supported monatomic cluster catalyst is characterized in that the catalyst is uniformly supported on a nitrogen-rich graphene aerogel carrier in a monatomic cluster form;
3. a pervasive preparation method of nitrogen-rich graphene aerogel supported monatomic cluster catalyst based on a sol-gel method is characterized by comprising the following steps:
1)g-C3N4the preparation of (1): the dicyandiamide or the melamine powder is subjected to pyrolysis in an inert gas atmosphere such as nitrogen, argon or helium, the decomposition temperature is 300-900 ℃, and the decomposition time is 40 min-6 h. Cooling to obtain g-C3N4A yellow powder;
2) preparation of graphene oxide GO: carrying out multi-step oxidation stripping treatment on graphite powder, and carrying out acid pickling, water washing and drying to obtain graphene oxide GO;
3) preparing nitrogen-enriched graphene hydrogel: ultrasonically dispersing the prepared graphene oxide in ultrapure water uniformly, adding a macrocyclic organic metal source precursor or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and a metal inorganic salt precursor and the prepared g-C3N4Ultrasonic, based on GO, g-C3N4And self-assembling and coordinating macrocyclic organic metal compound or nitrogenous macrocyclic compound to form uniform suspension, and then transferring the suspension into a high-temperature reaction kettle to perform hydrothermal reaction for a certain time to obtain nitrogen-rich graphene hydrogel;
4) preparing a nitrogen-enriched graphene aerogel supported monatomic cluster catalyst: and freeze-drying the hydrogel, and then performing high-temperature pyrolysis in an inert atmosphere to obtain the nitrogen-rich graphene aerogel supported monatomic cluster catalyst.
4. The preparation method of the nitrogen-enriched graphene aerogel supported monatomic cluster catalyst according to claim 3, characterized in that in the step 2), the preparation of graphene oxide GO is prepared by a multi-step oxidation exfoliation method of graphite powder. The method comprises the following steps:
a) 1-20 mL of concentrated H2SO4、03 to 5g of K2S2O8And 0.3 to 5g of P2O5And (3) fully mixing in an ice bath, adding 1-5 g of graphite powder into the mixed solution, and raising the temperature to 50-90 ℃ in an oil bath for pre-oxidation for 0.5-5 h. Then standing and cooling to room temperature, diluting with 0.3-1L of deionized water, filtering and collecting a solid product, continuously washing with deionized water to be neutral, and standing overnight and naturally drying for later use;
b) adding the solid product prepared in the step a) into concentrated H in 30-150 mL ice bath2SO4With concentrated H3PO4The mixed concentrated acid (volume ratio is 4-9: 1) is slowly added with 5-20 g of KMnO4Further oxidizing and keeping the temperature below 20 ℃ for 0.2-1 h, then heating to 30-45 ℃ for reaction for 1-6 h, diluting with 250-1000 mL of deionized water after reaction, and cooling to room temperature;
c) using 10-30 mL of 30 wt% H2O2Processing unreacted KMnO in the solution of step b)4Uniformly stirring until the reaction is finished, washing with a dilute HCl solution (1L), and then washing with deionized water until the reaction is neutral; and finally, carrying out vacuum drying to obtain the graphene oxide GO.
5. The preparation method of the nitrogen-enriched graphene aerogel supported monatomic cluster catalyst according to claim 3, characterized in that in step 3), the macrocyclic organometallic precursor is iron phthalocyanine, cobalt phthalocyanine or copper phthalocyanine; iron porphyrin, cobalt porphyrin or iron porphyrin; or a mixture of two thereof; or the nitrogen-containing macrocyclic compounds (azacrown ethers and macrocyclic polyamines) are mixed with iron nitrate, cobalt nitrate, copper nitrate or chloride, cobalt chloride, copper chloride or iron sulfate, cobalt sulfate, copper sulfate;
when the metal precursor is iron phthalocyanine or iron porphyrin or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and ferric nitrate or ferric chloride or ferric sulfate, the obtained catalyst material is a nitrogen-rich graphene aerogel supported iron-nitrogen cluster catalyst;
when the metal precursor is cobalt phthalocyanine or cobalt porphyrin or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and cobalt nitrate or cobalt ferric chloride or cobalt sulfate, the obtained catalyst material is a nitrogen-rich graphene aerogel supported cobalt-nitrogen atom cluster catalyst;
when the metal precursor is copper phthalocyanine or copper porphyrin or a nitrogen-containing macrocyclic compound (aza crown ether and macrocyclic polyamine) and copper nitrate or copper chloride or copper sulfate, the obtained catalyst material is a nitrogen-rich graphene aerogel supported copper nitrogen cluster catalyst;
when the metal precursor is an organic metal precursor mixture or a mixture of aza-crown ether, macrocyclic polyamine and metal inorganic salt, the obtained catalyst material is an atomic cluster catalyst of nitrogen-rich graphene aerogel supported mixed metal nitride.
6. The preparation of nitrogen-enriched graphene aerogel supported monatomic cluster catalyst according to claim 3, characterized in that in step 3), the preparation of nitrogen-enriched graphene hydrogel is carried out according to the following procedure:
adding 40 mg-0.5 g of GO prepared in the step 2) into 40-200 mL of ultrapure water for ultrasonic dispersion to obtain a yellow GO dispersion liquid; subsequently, an organometallic precursor or a nitrogen-containing macrocyclic compound (azacrown ether and macrocyclic polyamine) is combined with the metal inorganic salt precursor mixture and g-C3N4According to different GO: g-C3N4Adding metal precursors into GO dispersion liquid according to the mass ratio of 4:8:1, 3:6:1, 2:4:1, 1:2:1, 2:3:1 and 2:4.5:1, and carrying out ultrasonic treatment for 1-6 hours until the color of the solution changes from brown yellow to light green and finally to dark green. And then transferring the suspension into a proper high-temperature reaction kettle, carrying out hydrothermal treatment at 120-200 ℃ for 6-30 hours to obtain the nitrogen-rich graphene hydrogel.
7. The preparation method of the nitrogen-enriched graphene aerogel supported monatomic cluster catalyst according to claim 3, characterized in that in the step 4), the hydrogel obtained in the step 3) is freeze-dried for 24 hours; and then performing high-temperature pyrolysis for 1-4 h in nitrogen or argon or helium at the temperature of 500-950 ℃ to obtain the nitrogen-rich graphene aerogel supported monatomic cluster catalyst.
8. Nitrogen-enriched graphene aerogel supported monatomic cluster catalyst obtained by the method of any of claims 1-7.
9. The use of the nitrogen-enriched graphene aerogel supported monatomic cluster catalyst of claim 8, wherein: the nitrogen-rich graphene aerogel supported monatomic cluster catalyst is used for chemical reaction in an electrocatalytic alkaline solution and is used as an electrocatalyst.
10. Use according to claim 9, characterized in that: when the nitrogen-rich graphene aerogel supported monatomic cluster catalyst is a monatomic cluster catalyst containing one or more active sites of FeNx, CoNx and CuNx, the catalyst is used for catalyzing oxygen reduction (ORR) reaction of a fuel cell or a metal-air cell and OER reaction of electrolyzed water under an alkaline condition.
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| CN113559911A (en) * | 2021-07-30 | 2021-10-29 | 中国科学院生态环境研究中心 | Monoatomic catalyst, preparation method and application thereof |
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