CN112473714A - Composite material loaded with metal monoatomic, preparation method and application thereof - Google Patents
Composite material loaded with metal monoatomic, preparation method and application thereof Download PDFInfo
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- CN112473714A CN112473714A CN202011348536.4A CN202011348536A CN112473714A CN 112473714 A CN112473714 A CN 112473714A CN 202011348536 A CN202011348536 A CN 202011348536A CN 112473714 A CN112473714 A CN 112473714A
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- composite material
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- monoatomic
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 144
- 239000002184 metal Substances 0.000 title claims abstract description 144
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 53
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 20
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 49
- 238000009987 spinning Methods 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000001523 electrospinning Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002505 iron Chemical class 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
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- -1 dicyanodiamine Chemical compound 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 32
- 239000002086 nanomaterial Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002121 nanofiber Substances 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001816 cooling Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000003763 carbonization Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000014509 gene expression Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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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- B01J35/33—
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- B01J35/391—
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- B01J35/393—
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- B01J35/399—
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- B01J35/58—
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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
- 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
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/12—Oxidising
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- 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
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- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—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
Abstract
The application belongs to the technical field of nano materials, and particularly relates to a composite material loaded with metal monoatomic atoms, a preparation method of the composite material and application of the composite material loaded with metal monoatomic atoms. The preparation method of the composite material loaded with metal monoatomic atoms comprises the steps of preparing mixed precursor slurry of a polymer, metal salt, an organic nitrogen source and an organic solvent; performing electrostatic spinning on the mixed precursor slurry to obtain mixed precursor protofilaments; pre-oxidizing the mixed precursor, and then carbonizing to obtain a carbonized product; and carrying out acid oxidation treatment on the carbonized product, and separating to obtain the composite material loaded with the metal monoatomic atoms. The preparation method of the composite material loaded with the metal monoatomic atoms is simple in process, mild and safe in condition and suitable for industrial large-scale production and application. The metal monoatomic group in the prepared composite material is uniformly and stably loaded in the carbon nanofiber, so that the composite material is good and stable in catalytic effect.
Description
Technical Field
The application belongs to the technical field of nano materials, and particularly relates to a composite material loaded with metal monoatomic atoms, a preparation method of the composite material and application of the composite material loaded with metal monoatomic atoms.
Background
The 'hydrogen production by water electrolysis-fuel cell power generation' mode is considered to be an important link for clean and efficient utilization of renewable energy. Hydrogen production by electrolysis of water and fuel cells both involve electrochemical reactions of Oxygen, namely Oxygen Evolution Reaction (OER) and Oxygen Reduction Reaction (ORR). For OER, only noble metal catalysts, such as IrO, can be used due to its slow kinetics and complex reaction mechanism2And RuO2. The precious metal catalyst is low in storage amount, so that the cost of water electrolysis equipment is high. In recent years, transition metal oxides, nitrides and carbides such as perovskites and pyrochlores have also been used in acidic electrolyzed water, but further improvement in catalytic performance and stability is required. For the ORR reaction, the kinetics are slow, the reaction mechanism is not clear, and only Pt/C or PtxM/C alloy catalysts can be used. And the storage amount of the noble metal platinum is small, so that the platinum is easy to poison in the working environment, and the large-scale industrialization of the fuel cell is limited. Therefore, the designed OER and ORR catalysts have important application value for improving the performance of the electrolytic water and fuel cell equipment and obviously reducing the cost.
In recent years, the preparation and application of monatomic catalysts have received much attention. The basic idea is to further disperse nano-sized catalyst particles into single atoms, thereby improving the utilization rate of noble metal atoms to the maximum extent, improving the catalytic activity and reducing the dosage of noble metals. Meanwhile, compared with the traditional nano catalyst, the single-atom catalyst has higher reaction selectivity and can improve the efficiency of OER and ORR. Common methods for preparing monatomic catalysts are: coprecipitation, impregnation, displacement, atomic layer deposition, soft landing, and the like. However, these methods have the problems of harsh experimental conditions, high cost, poor stability, low loading capacity and the like, and the prepared catalyst cannot form a self-supporting electrode.
Disclosure of Invention
The application aims to provide a composite material loaded with metal monoatomic atoms, a preparation method thereof, and a method for preparing hydrogen by using the composite material in fuel cells and water electrolysis, and aims to solve the problems of severe conditions, high cost, poor stability of the prepared catalyst and low loading capacity of the existing preparation method of the monoatomic catalyst to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a metal monoatomic-supported composite material,
preparing mixed precursor slurry of a polymer, a metal salt, an organic nitrogen source and an organic solvent;
performing electrostatic spinning on the mixed precursor slurry to obtain mixed precursor protofilaments;
pre-oxidizing the mixed precursor, and then carbonizing to obtain a carbonized product;
and carrying out acid oxidation treatment on the carbonized product, and separating to obtain the composite material loaded with the metal monoatomic atoms.
In a second aspect, the present application provides a metal monoatomic composite material including a carbon nanofiber and a nitrogen element doped on the carbon nanofiber and a metal monoatomic supported on the carbon nanofiber.
In a third aspect, the application provides an application of the composite material loaded with metal monoatomic atoms, and the composite material loaded with metal monoatomic atoms prepared by the method or the composite material loaded with metal monoatomic atoms is applied to a fuel cell or hydrogen production by electrolyzing water.
The preparation method of the metal monoatomic-supported composite material provided by the first aspect of the application is simple in process, mild and safe in conditions, and suitable for industrial large-scale production and application. The metal monoatomic atoms in the prepared composite material are uniformly and stably loaded in the carbon nanofibers, so that the composite material loaded with the metal monoatomic atoms has a good and stable catalytic effect.
The composite material loaded with the metal monoatomic atoms provided by the second aspect of the application takes the carbon nanofibers as carriers, and the metal monoatomic atoms are uniformly and stably loaded on the carbon nanofibers, so that the composite material loaded with the metal monoatomic atoms has high catalytic activity and stability. The doped nitrogen element improves the load stability of the metal monoatomic atoms on the carbon nano fibers, so that the composite material loaded with the metal monoatomic atoms has more stable catalytic activity.
In the third aspect of the application, the composite material loaded with the metal monoatomic atoms has high catalytic activity and stability, can be used as a self-supporting electrode in the fields of hydrogen production by water electrolysis, fuel cells and the like, and particularly can be used as a catalyst for oxygen reduction reaction, so that the dosage of a noble metal catalyst can be reduced while the catalytic activity of the oxygen reduction reaction and the material transmission of a catalyst layer are ensured, and the utilization rate of the catalyst is improved. Moreover, the carbon nano fiber can protect the metal monoatomic atom loaded by the carbon nano fiber, and the corrosion of electrolyte and the like to the metal monoatomic atom is avoided, so that the working efficiency and the stability of hydrogen production by water electrolysis or a fuel cell are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing a metal monoatomic-supported composite material provided in an embodiment of the present application;
fig. 2 is a Scanning Electron Microscope (SEM) image of the Pt-loaded monoatomic nanofiber provided in example 1 of the present application;
FIG. 3 is a Transmission Electron Micrograph (TEM) of the Pt monoatomic nanofiber prepared in example 1 of the present application;
fig. 4 is a graph of oxygen reduction linear polarization of Pt-monatomic loaded nanofibers provided in example 1 of the present application.
FIG. 5 is a Transmission Electron Micrograph (TEM) of the Ru monoatomic loaded nanofiber provided in comparative example 1 of the present application;
FIG. 6 is a graph of oxygen reduction linear polarization of Ru monatomic loaded nanofibers provided in comparative example 1 of the present application;
FIG. 7 is a Scanning Electron Microscope (SEM) image of Pt monoatomic loaded nanofibers provided in comparative example 2 of the present application;
FIG. 8 is a graph of oxygen reduction linear polarization of Pt monoatomic nanofiber as provided in comparative example 2 of the present application;
FIG. 9 is a Scanning Electron Microscope (SEM) image of Pt monoatomic loaded nanofibers provided in comparative example 3 of the present application;
fig. 10 is a graph of oxygen reduction linear polarization of Pt-loaded monoatomic nanofibers provided in comparative example 3 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In the present invention, the term "and/or" describes the association relationship of the associated objects, and means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present invention, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the mass in the description of the embodiments of the present invention may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the invention. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in the attached FIG. 1, the first aspect of the embodiments of the present application provides a method for preparing a metal monoatomic composite material,
s10, preparing mixed precursor slurry of a polymer, a metal salt, an organic nitrogen source and an organic solvent;
s20, performing electrostatic spinning on the mixed precursor slurry to obtain mixed precursor protofilaments;
s30, carrying out pre-oxidation treatment on the mixed precursor, and then carrying out carbonization treatment to obtain a carbonized product;
and S40, carrying out acid oxidation treatment on the carbonized product, and separating to obtain the composite material loaded with the metal monoatomic atoms.
According to the preparation method of the composite material loaded with the metal monoatomic atoms, provided by the application, a mixed precursor slurry of a polymer, a metal salt, an organic nitrogen source and an organic solvent is used as a raw material, after a precursor is formed through electrostatic spinning, dehydrogenation, oxidation and cyclization reactions are carried out through pre-oxidation treatment, a trapezoidal polymer structure is formed, and carbon fibers are preliminarily shaped; and then the carbon fiber is solidified and molded through carbonization treatment to obtain a stable carbonized product. And then removing redundant byproducts in the carbon fibers through acid oxidation treatment to obtain the composite material loaded with metal monoatomic atoms. The preparation method of the metal monoatomic-supported composite material provided by the embodiment of the application is simple in process, mild and safe in condition and suitable for industrial large-scale production and application. The metal monoatomic atoms in the prepared composite material are uniformly and stably loaded in the carbon nanofibers, so that the composite material loaded with the metal monoatomic atoms has a good and stable catalytic effect. In addition, the organic nitrogen source raw material components in the mixed precursor slurry play roles of in-situ doping and in-situ pore forming on the carbon material simultaneously in the preparation process, so that on one hand, the pore forming is favorable for improving the effective specific surface area of the carbon nano material, is more favorable for metal atom loading doping and improves the loading capacity of metal single atoms; on the other hand, the doped nitrogen element can be coordinated with the metal atom to form a stable composite structure of the metal nitrogen atom-nitrogen element-carbon nanofiber, namely an M-N-C structure, so that the metal atom is more uniformly and stably distributed in the nanomaterial, the metal monoatomic atom is enabled to realize more uniform and stable doping effect, and the catalytic effect of the composite material loaded with the metal monoatomic atom is further ensured.
Specifically, in step S10, the step of preparing the mixed precursor slurry includes: and mixing the polymer, the metal salt, the organic nitrogen and the organic solvent at the temperature of 80-100 ℃ to obtain mixed precursor slurry. The polymer is carbonized at high temperature to become carbon fiber, which provides a carrier for the load of metal single atoms; the metal salt provides metal single atoms for the nano material, so that the nano material has catalytic activity; the organic nitrogen source can play a role in pore forming and doping on the nano material at the subsequent pre-oxidation and carbonization treatment stages, so that metal single atoms are more uniformly and stably combined on the carbon nano material, and the catalytic stability of the nano material is improved. Wherein the mixing temperature of 80-100 ℃ enables the polymer, the metal salt and the organic nitrogen source to be more efficiently and fully dissolved in the organic solvent to form stable and uniform mixed precursor slurry. If the temperature is too low, the raw material components such as the polymer and the like are slowly dissolved; if the temperature is too high, the solvent evaporates, resulting in a change in viscosity and affecting the spinning quality.
In some embodiments, the mixed precursor slurry has a polymer mass concentration of 5 to 20%, a metal salt mass concentration of 1 to 30%, and an organic nitrogen source mass concentration of 0.1 to 10%. The polymer concentration can influence the viscosity of the mixed precursor slurry, and the polymer with the mass concentration of 5-20% enables the viscosity of the mixed precursor slurry to be suitable for subsequent electrostatic spinning. If the concentration is too low, the viscosity is too low to form filaments in the subsequent electrospinning step. If the viscosity is too high, the stainless steel needle is easy to block during electrostatic spinning, and the feasibility is poor. The catalytic activity and the catalytic stability of the nano material are effectively ensured by the metal salt with the mass concentration of 1-30%, if the solubility of the metal salt is too high, the surface metal of the finally formed carbon nano fiber is loaded more, metal single atoms are easy to agglomerate into nano particles instead of the metal single atoms, and the catalytic activity is low. The organic nitrogen source with the mass concentration of 0.1-10% is beneficial to doping and pore-forming of a nitrogen source on the carbon nano material, and the mixed precursor slurry has proper viscosity, if the concentration of the nitrogen source is low, the nitrogen doping efficiency on the carbon nano fiber material is too low, the pore-forming effect is not good, and the uniform and stable loading of metal single atoms is not facilitated; if the concentration of the nitrogen source is too high, the viscosity of the mixed precursor slurry is too high, the subsequent electrostatic spinning is not facilitated, and normal protofilaments cannot be formed. In some embodiments, the mass concentration of the polymer in the mixed precursor slurry is 5% to 10%, 10% to 15%, 15% to 20%, or the like; the mass concentration of the metal salt is 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30% and the like; the mass concentration of the organic nitrogen source is 0.1-1%, 1-5%, 5-10% and the like.
In some embodiments, the polymer is selected from: at least one of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyvinyl butyral and polyimide; the polymers can form carbon nanofibers in the subsequent pre-oxidation and carbonization high-temperature stages, and provide a carrier for the load of metal single atoms; but also can play a role in dispersing metal salt, and can synthesize the uniformly dispersed nano-fiber composite material loaded with metal monoatomic atoms more easily. In some embodiments, the polymer is selected from polyacrylonitrile with a molecular weight of 8 to 30 ten thousand, and the polyacrylonitrile contains nitrogen element, so that carbon nano fiber doped with nitrogen element can be formed, and the nitrogen element can form coordination with metal atoms in the mixed precursor slurry, so that the metal salt is dispersed in the solution more uniformly and stably.
In some embodiments, the metal salt is selected from: at least one of platinum salt, cobalt salt, iron salt and nickel salt, wherein the metal salt can provide metal monoatomic atoms of platinum, iron, cobalt, nickel and the like for the nano material, and the metal monoatomic atoms have higher catalytic reaction activity on oxygen reduction reaction.
In some embodiments, the platinum salt is selected from: at least one of platinum acetylacetonate, platinum chloride and platinum nitrate. In some embodiments, the cobalt salt is selected from: at least one of cobalt acetylacetonate, cobalt chloride and cobalt nitrate. In some embodiments, the iron salt is selected from: at least one of ferric acetylacetonate, ferric chloride and ferric nitrate. In some embodiments, the nickel salt is selected from: at least one of nickel acetylacetonate, nickel chloride and nickel nitrate. The metal salts adopted in the embodiments of the present application have good solubility in organic solvents, which is beneficial to forming uniform and stable mixed precursor slurry. Meanwhile, the decomposition temperature of the metal salts is low, and particularly, the acetylacetone metal salts can be stably decomposed to form metal single atoms in the subsequent pre-oxidation and carbonization treatment stages.
In some embodiments, the organic nitrogen source is selected from: at least one of cyanamide, dicyanodiamine, melamine, ethylenediamine and urea; the organic nitrogen sources can decompose and generate ammonia gas in situ in the subsequent pre-oxidation and carbonization stages, so that the in-situ pore forming can be performed on the carbon nano-fiber, the effective specific surface area of the carbon nano-fiber is increased, and the uniform loading of metal single atoms is facilitated; and nitrogen elements can be uniformly doped in the carbon nano material in situ, and the metal atoms are more stably loaded in the carbon nano material through coordination of the nitrogen elements and the metal atoms, so that the metal monoatomic-loaded composite material with high catalytic activity and high stability is formed. According to the embodiment of the application, the organic nitrogen source is added into the precursor solution in the form of raw materials, and then electrostatic spinning, pre-oxidation, carbonization and other treatment are carried out, so that in-situ pore forming and nitrogen doping are realized, the doping and pore forming effects are good, the experimental safety is high, the condition and the temperature are high, and the potential hazard caused by directly using ammonia gas is avoided.
In some embodiments, the organic solvent is selected from: the organic solvents have better solubility to polymers, metal salts and organic nitrogen sources, are beneficial to dissolving and mixing various raw material components to form uniform and stable precursor solution, and are convenient for subsequent electrostatic spinning.
Specifically, in step S20, the step of electrospinning includes: and adding the mixed precursor slurry into a spinning injector, introducing 12-20 kV positive voltage to the spinning injector, introducing 0-5 kV negative voltage to a spinning receiving matrix, spinning under the conditions that the distance between a needle of the spinning injector and the spinning receiving matrix is 15-20 cm, the electric field intensity is 0.5-2 kV/cm, and the rotating speed of the spinning receiving matrix is 100-500 rpm, and forming mixed precursor protofilaments on the spinning receiving matrix. This application embodiment adopts the electrostatic spinning technique to spin mixed precursor thick liquids, after adding mixed precursor thick liquids to the spinning syringe, lead to the positive voltage to the spinning syringe, receive the base member to the spinning and lead to the negative voltage, when mixed precursor fluid is released the injector spinning jet, because plus high voltage on the spinning jet, make liquid drop surface carry the homogeneous charge, can offset the surface tension effect, make the liquid at first form the taylor vertebra after spouting, under the combined action of surface charge repulsion and strong electric field, the efflux diameter descends by a wide margin, the efflux diameter is more and more littleer, the solvent volatilizes, finally, receive the mixed precursor of formation superfine diameter on the base member at the spinning. Wherein, the distance between the needle of the spinning injector and the spinning receiving matrix is 15 cm-20 cm, the electric field intensity is 0.5 kV/cm-2 kV/cm, and the rotating speed of the spinning receiving matrix is 100rpm-500rpm, thereby effectively ensuring the electrostatic spinning effect. Under the same electric field intensity, the applied static voltage is too high due to too large distance, so that the risk exists, and the precursor can fall too early and cannot be collected due to too large distance. The stacking of the protofilaments is easily caused by too low rotating speed; too high a rotational speed tends to cause the strands to easily tear. In some embodiments, a positive voltage of 12kV to 15kV, 15kV to 17kV or 17kV to 20kV is applied to the spinning injector, a negative voltage of 0 to-1 kV, -1 to-2 kV, -2 to-3 kV, -3 to-4 kV or-4 to-5 kV is applied to the spinning receiving matrix, the distance between the needle of the spinning injector and the spinning receiving matrix is 15cm, 16cm, 17cm, 18cm, 19cm or 20cm, the electric field strength is 0.5kV/cm to 1kV/cm, 1kV/cm to 1.5kV/cm or 1.5kV/cm to 2kV/cm, and the rotating speed of the spinning receiving matrix is 100rpm to 200rpm, 200rpm to 300rpm, 300rpm to 400rpm or 400rpm to 500 rpm.
In some embodiments, the spinning injector has a needle head with an inner diameter of 0.8mm to 1.1mm, which is advantageous for spinning to form small and uniform-diameter strands, and provides a basis for subsequently preparing the metal monoatomic-supported composite material. In some embodiments, the spinning syringe has a needle inner diameter of 0.8mm, 0.9mm, 1mm, or 1.1mm, among others.
In some embodiments, the ambient temperature of the electrostatic spinning is 20-30 ℃, and the relative humidity is 10-50%, wherein if the temperature is too low, the volatilization speed of the solvent is affected, and if the temperature is too high, the solvent is prematurely volatilized, and then is solidified to block the needle head; if the temperature is too low, the prepared strands may be dissolved. In addition, under otherwise normal conditions and high humidity, it is possible that water will concentrate on the fiber surface as the electrospinning proceeds, thereby affecting the fiber morphology, and especially the fibers are susceptible to such effects as electrospinning polymers dissolved in volatile solvents. In the case of too low a humidity, the solvent will evaporate and dry quickly, and the solvent may evaporate faster than it can be removed from the needle, thereby causing the needle to be clogged, and the electrospinning process can last for only a few minutes. In some embodiments, the ambient temperature of the electrospinning is 20-25 ℃, 25-30 ℃ or the like, and the relative humidity is 10-20%, 20-30%, 30-40%, 40-50% or the like.
In some embodiments, after the mixed precursor slurry is added into the spinning injector, a positive voltage of 12kV to 20kV is applied to the spinning injector, a negative voltage of 0kV to-5 kV is applied to the spinning receiving matrix, spinning is carried out under the conditions that the distance between the needle head of the spinning injector and the spinning receiving matrix is 15cm to 20cm, the electric field intensity is 0.5kV/cm to 2kV/cm, the rotating speed of the spinning receiving matrix is 100rpm to 500rpm, the ambient temperature is 20 ℃ to 30 ℃, and the relative humidity is 10% to 50%, so that the mixed precursor protofilament is formed on the spinning receiving matrix.
Specifically, in step S30, the pre-oxidation process includes: heating the precursor mixture to 200-300 ℃ in the air atmosphere with the heating rate of 0.5-5 ℃/min, and then preserving the heat for 1-5 h. This application embodiment is through carrying out the pre-oxidation treatment to the precursor, makes the precursor carry out dehydrogenation, oxidation and cyclization reaction, tentatively stereotypes the carbon fiber, forms trapezoidal polymer structure. The temperature rise rate of the pre-oxidation treatment needs to be kept in a low range, and too fast temperature rise can cause rapid melting of the protofilament in the pre-oxidation process, so that the fiber appearance is seriously damaged. The heat preservation temperature of 200-300 ℃ effectively ensures the primary shaping of the protofilament, if the temperature is too high, the protofilament generates combustion reaction, and the product cannot be obtained. The heat preservation time is 1-5 h, and the complete pre-oxidation of the fiber can be basically ensured.
Specifically, in step S30, the carbonization step includes: and under the inert atmosphere with the heating rate of 0.5-5 ℃/min, heating the product after the pre-oxidation treatment to 800-1200 ℃, and then preserving the heat for 0.5-5 h. Fully carbonizing the pre-oxidized protofilament under the condition to carbonize the polymer in the protofilament to form a carbon nano material; decomposing the organic nitrogen source at high temperature to form ammonia gas, and carrying out pore-forming and nitrogen doping on the carbon nano material; the metal salt is decomposed at high temperature to form metal monoatomic, and finally the carbonized crude product of the composite material loaded with the metal monoatomic is obtained. If the carbonization temperature is too high and the temperature rise rate is too fast, the raw material components are decomposed too fast, and the morphology of the nano material is possibly damaged.
Specifically, in step S40, the acid oxidation treatment includes: according to the proportion of the mass of the carbonized product to the volume of the oxidizing acid solution of 1 mg: (1-10) mL, mixing the carbonized product with an oxidizing acid solution, reacting for 2-8 h at the temperature of 80-120 ℃, separating and drying to obtain the composite material loaded with the metal monoatomic atoms. According to the embodiment of the application, the carbonized product is subjected to acid oxidation treatment, and unreduced metal salt and generated byproducts are removed, so that the composite material loaded with metal monoatomic atoms is obtained. Wherein the ratio of the mass of the carbonized product to the volume of the oxidizing acid solution is 1 mg: and (1-10) mL, so that the acidic solution can completely remove the unreduced metal salt and the by-product in the carbonized product. The reaction is carried out for 2 to 8 hours at the temperature of between 80 and 120 ℃, the oxidation effect and the oxidation rate are fully ensured, and if the temperature is too high and the time is too long, the carbon fiber can be oxidized in a large scale, the fiber is broken, and the structure of the nano material is damaged.
In some embodiments, the oxidizing acid solution is selected from: at least one of sulfuric acid, nitric acid and hydrochloric acid. In some embodiments, the oxidizing acid solution has a concentration of 1mol/L to 6 mol/L. The oxidizing acid solution and the concentration of the acid solution in the above embodiments of the present application have a good oxidation removal effect on unreduced metal salts and byproducts in the carbonized product, and if the concentration of the acid solution is too high, the structure of the nanomaterial may be damaged.
In a second aspect, the present embodiment provides a metal monoatomic composite material prepared by the above method, where the metal monoatomic composite material includes a carbon nanofiber and a nitrogen element doped in the carbon nanofiber, and a metal monoatomic supported on the carbon nanofiber.
The composite material loaded with the metal monoatomic atoms provided by the second aspect of the application takes the carbon nanofibers as carriers, and the metal monoatomic atoms are uniformly and stably loaded on the carbon nanofibers, so that the composite material loaded with the metal monoatomic atoms has high catalytic activity and stability. The doped nitrogen element improves the load stability of the metal monoatomic atoms on the carbon nano fibers, so that the composite material loaded with the metal monoatomic atoms has more stable catalytic activity.
In some embodiments, the metal monoatomic composite material has a metal monoatomic loading of 0.1 wt% to 20 wt%, which is effective to ensure the catalytic activity of the metal monoatomic composite material, and if the loading is too low, the catalytic activity is low, and if the loading is too high, too many metal atoms are easily aggregated and fused to form metal particles, which also reduces the catalytic activity of the metal monoatomic composite material. In some embodiments, the metal monoatomic composite material is loaded with 0.1 wt% to 1 wt%, 1 wt% to 5 wt%, 5 wt% to 10 wt%, 15 wt% to 20 wt%, etc.
In some embodiments, the diameter of the composite material loaded with the metal monoatomic atoms is 100-300 nm, and the small and uniform nanofibers have a larger effective specific surface area, so that the uniform loading of the metal monoatomic atoms is facilitated, and the catalytic activity and stability of the composite material loaded with the metal monoatomic atoms are improved. In some embodiments, the metal-monoatomic composite material has a diameter of 100 to 150nm, 150 to 200nm, 200 to 250nm, 250 to 300nm, or the like.
In some embodiments, the loading of nitrogen in the metal monatomic loaded composite material is between 0.1 wt% and 10 wt%. The nitrogen element doped in the composite material loaded with the metal monoatomic atoms can improve the loading efficiency of the metal monoatomic atoms on the nano fibers and can improve the catalytic activity and stability of the composite material loaded with the metal monoatomic atoms. The nitrogen element with the loading amount of 0.1-10 wt% effectively ensures the loading effect of metal single atoms on the nano-fibers.
The composite material loaded with the metal monoatomic atoms can be used as an oxygen reduction reaction catalyst, and the composite material loaded with the metal monoatomic atoms has a large effective specific surface area, so that the metal monoatomic atoms are uniformly and stably loaded, and the nano material has high catalytic activity. The composite material loaded with the metal monoatomic atoms effectively solves the problems of metal monoatomic atom agglomeration, low load capacity and the like.
In a third aspect of the embodiments of the present application, there is provided an application of a metal-monatomic-supported composite material, where the metal-monatomic-supported composite material prepared by the above method or the metal-monatomic-supported composite material is applied to a fuel cell or hydrogen production by electrolyzing water.
In the third aspect of the application, the composite material loaded with the metal monoatomic atoms has high catalytic activity and stability, can be used as a self-supporting electrode in the fields of hydrogen production by water electrolysis, fuel cells and the like, and particularly can be used as a catalyst for oxygen reduction reaction, so that the dosage of a noble metal catalyst can be reduced while the catalytic activity of the oxygen reduction reaction and the material transmission of a catalyst layer are ensured, and the utilization rate of the catalyst is improved. Moreover, the carbon nano fiber can protect the metal monoatomic atom loaded by the carbon nano fiber, and the corrosion of electrolyte and the like to the metal monoatomic atom is avoided, so that the working efficiency and the stability of hydrogen production by water electrolysis or a fuel cell are improved.
In order to clearly understand the details and operation of the above-mentioned embodiments of the present application by those skilled in the art, and to obviously show the advanced performance of the metal-loaded monatomic composite material and the preparation method and application thereof in the examples of the present application, the above-mentioned technical solution is exemplified by a plurality of examples below.
Example 1
A Pt monoatomic nano-fiber is prepared by the following steps:
dissolving polyacrylonitrile PAN (4.5g), platinum acetylacetonate (0.45g) and cyanamide (the mass fraction is 50%, 89 mu L) in 45g of N-N dimethylformamide solution to obtain a precursor solution.
Adjusting equipment parameters: the high voltage is 16kV, and the low voltage is-2 kV. The solution flow rate was 0.5mL/min, the spinning distance was 16cm, and the receiver rotation speed was 200 rpm. And selecting a No. 17 stainless steel needle for spinning. Keeping the environmental humidity within 30 percent and continuously ventilating warm air. Continuously electrospinning for 40h to obtain precursor;
thirdly, the protofilament is paved and fixed in a muffle furnace, the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min, pre-oxidation is carried out for 2h, and then natural cooling is carried out. Then, transferring the preoxidized product to a vacuum tube furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under the protection of argon inert gas, preserving heat for 1h, and then cooling to room temperature at a cooling rate of-5 ℃/min to obtain a carbonized product;
and fourthly, placing the carbonized product obtained in the third step in 4mol/L nitric acid, heating for 6 hours at the temperature of 120 ℃, naturally cooling, repeatedly washing with deionized water, and then drying in a vacuum drying oven at the temperature of 120 ℃ to obtain the Pt monoatomic loaded nanofiber.
Example 2
A Fe monoatomic-supported nanofiber comprises the following preparation steps:
[ solution ] PAN (4.5g), ferrous acetylacetonate (0.37g) and urea (0.083g) were dissolved in 45g of an N-methylpyrrolidone solution to obtain a precursor solution.
And secondly, carrying out electrostatic spinning to obtain protofilaments, wherein the equipment parameters are as in example 1.
Thirdly, the protofilament is paved and fixed in a muffle furnace, the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min, pre-oxidation is carried out for 2h, and then natural cooling is carried out. Then transferring the preoxidized product to a vacuum tube furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, preserving heat for 1h, and then cooling to room temperature at a cooling rate of-5 ℃/min to obtain a carbonized product;
and fourthly, placing the product obtained in the third step in 6mol/L nitric acid, heating for 6 hours at the temperature of 120 ℃, naturally cooling, repeatedly washing with deionized water, and then drying in a vacuum drying oven at the temperature of 120 ℃ to obtain the Fe monatomic-loaded nanofiber.
Example 3
A Co monoatomic-supported nanofiber comprises the following preparation steps:
[ solution ] PAN (4.5g), cobalt acetylacetonate (0.39g) and ethylenediamine (0.065g) were dissolved in 45g of a dimethyl sulfoxide solution to obtain an electrospinning solution.
And secondly, carrying out electrostatic spinning to obtain protofilaments, wherein the equipment parameters are as in example 1.
Thirdly, the protofilament is paved and fixed in a muffle furnace, the temperature is raised to 250 ℃ at the heating rate of 1 ℃/min, pre-oxidation is carried out for 2h, and then natural cooling is carried out. Then, transferring the preoxidized product to a vacuum tube furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, preserving heat for 1h, and then cooling to room temperature at a cooling rate of-5 ℃/min to obtain a carbonized product;
putting the product obtained in the step (III) into 6mol/L nitric acid, heating for 6h at 120 ℃, naturally cooling, repeatedly washing with deionized water, and drying in a vacuum drying oven at 120 ℃ to obtain the Co monoatomic-loaded nanofiber.
Comparative example 1
The comparison example is used for preparing the Ru monatomic loaded nanofiber catalyst, and aims to compare the catalytic performances of the Ru monatomic nanofiber catalyst and the Pt, Fe and Co monatomic nanofiber catalysts of examples 1-3 of the application. It differs from example 1 in that: the Pt source used in example 1 was replaced with ruthenium trichloride.
Comparative example 2
The comparison example prepares the single-atom-loaded nanofiber catalyst doped with nitrogen by ammonia, and aims to research the influence of different nitrogen doping modes on the final catalytic activity of the material. It differs from example 1 in that: adding no cyanamide; secondly, heating the pre-oxidized fiber to 700-1000 ℃ at the heating rate of 5 ℃/min in the ammonia atmosphere, and preserving the temperature for 1h to obtain a carbonized product.
Comparative example 3
The present comparative example consists in preparing a nanofibrous catalyst with a metal content higher than 20 wt% with the aim of studying the catalytic activity of the catalyst at high loading. It differs from example 1 in that: the amount of platinum acetylacetonate added in step (i) was only 2.0 g.
Further, in order to verify the advancement of the composite material supporting metal monoatomic atoms of the examples of the present application, the following performance test was performed on the monoatomic-supported nanofibers prepared in example 1.
1. The morphology of the monoatomic-supported nanofibers prepared in example 1 was tested by SEM and TEM. As shown in the SEM image of attached figure 2, the prepared monatomic-loaded nanofiber has the tube diameter of 100-300 nm, small tube diameter, high uniformity and large effective specific surface area, and is beneficial to improving the catalytic activity of the nanomaterial. As shown in a TEM image of attached figure 3, the Pt monoatomic load in the nanofiber has extremely small particle size, the load in a monoatomic form is realized, and simultaneously, metal atoms are uniformly distributed in the nanomaterial, so that the catalytic activity and the stability of the material are effectively improved, and the utilization rate of noble metals is improved.
2. The monoatomic-supported nanofiber prepared in example 1 was tested for oxygen reduction and the test results are shown in fig. 4, in which the abscissa represents voltage and the ordinate represents current density. The test is carried out in a rotating disc device, and RDE with radius of 5mm and rotation speed of 20mv s is adopted-1The scan direction goes from a negative potential to a positive potential. The test provides quantitative data for the catalytic activity of the material, and can be used for comparing the performance of the material with that of other materials.
3. The morphology of the monoatomic-loaded nanofiber prepared in comparative example 1 was characterized and the oxygen reduction performance thereof was tested. FIG. 5 is an electron micrograph showing that large particles are present, and this shows that the Ru metal is agglomerated more severely under the conditions of comparative example 1, which results in poor oxygen reduction performance. Oxygen gasThe reduction test results are shown in fig. 6, in which the abscissa is voltage and the ordinate is current density. The test is carried out in a rotating disc device, and RDE with radius of 5mm and rotation speed of 20mv s is adopted-1The scan direction goes from a negative potential to a positive potential. Comparing it with fig. 4, it shows significantly worse performance than example 1, thus demonstrating that Ru-based nanofibers perform relatively poorly.
4. The application tests the oxygen reduction performance of the monoatomic-loaded nanofiber prepared in comparative example 2 and characterizes the morphology of the monoatomic-loaded nanofiber. FIG. 7 is an electron micrograph showing fiber breakage, which is a phenomenon that the ammonia treatment causes breakage of the prepared carbon fiber. The results of the oxygen reduction test are shown in FIG. 8, where the abscissa is voltage and the ordinate is current density. The test is carried out in a rotating disc device, and RDE with radius of 5mm and rotation speed of 20mv s is adopted-1The scan direction goes from a negative potential to a positive potential. Comparing it with figure 4, it is demonstrated that the nanofibers prepared under ammonia conditions are relatively poor in performance.
5. The morphology of the monoatomic-loaded nanofiber prepared in comparative example 3 was characterized and the oxygen reduction performance thereof was tested. FIG. 9 is an electron micrograph showing that large particles are present, indicating that the Pt metal is more strongly agglomerated at higher loadings. The results of the oxygen reduction test are shown in fig. 10, in which the abscissa represents voltage and the ordinate represents current density, and the abscissa represents voltage and the ordinate represents current density. The test is carried out in a rotating disc device, and RDE with radius of 5mm and rotation speed of 20mv s is adopted-1The scan direction goes from a negative potential to a positive potential. Comparing it with figure 4, it shows significantly worse performance than example 1, thus demonstrating that agglomeration of Pt results in poor fiber performance at loadings greater than 20 wt%.
The above description is only for the purpose of illustrating preferred embodiments and comparative examples, and is not intended to limit the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the scope of the present application.
Claims (10)
1. A preparation method of a composite material loaded with metal monoatomic atoms is characterized in that,
preparing mixed precursor slurry of a polymer, a metal salt, an organic nitrogen source and an organic solvent;
performing electrostatic spinning on the mixed precursor slurry to obtain mixed precursor protofilaments;
pre-oxidizing the mixed precursor, and then carbonizing to obtain a carbonized product;
and carrying out acid oxidation treatment on the carbonized product, and separating to obtain the composite material loaded with the metal monoatomic atoms.
2. The method for preparing a metal-monoatomic-supported composite material according to claim 1, wherein the mixed precursor slurry contains the polymer in a mass concentration of 5 to 20%, the metal salt in a mass concentration of 1 to 30%, and the organic nitrogen source in a mass concentration of 0.1 to 10%;
and/or, the polymer is selected from: at least one of polyacrylonitrile, polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, polyvinyl butyral and polyimide;
and/or, the metal salt is selected from: at least one of platinum salt, cobalt salt, iron salt and nickel salt;
and/or, the organic nitrogen source is selected from: at least one of cyanamide, dicyanodiamine, melamine, ethylenediamine and urea;
and/or, the organic solvent is selected from: at least one of N-N dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
3. The method of preparing a metal monatomic-loaded composite material according to claim 2, wherein the platinum salt is selected from the group consisting of: at least one of platinum acetylacetonate, platinum chloride and platinum nitrate;
and/or, the cobalt salt is selected from: at least one of cobalt acetylacetonate, cobalt chloride and cobalt nitrate;
and/or, the iron salt is selected from: at least one of ferric acetylacetonate, ferric chloride and ferric nitrate;
and/or, the nickel salt is selected from: at least one of nickel acetylacetonate, nickel chloride and nickel nitrate.
4. The method for preparing a metal-monatomic-supported composite material according to any one of claims 1 to 3, wherein the step of preparing the mixed precursor slurry comprises: mixing the polymer, the metal salt, the organic nitrogen source and the organic solvent at the temperature of 80-100 ℃ to obtain mixed precursor slurry;
and/or the step of electrospinning comprises: adding the mixed precursor slurry into a spinning injector, then introducing 12 kV-20 kV positive voltage to the spinning injector, introducing 0-5 kV negative voltage to a spinning receiving matrix, spinning under the conditions that the distance between a needle head of the spinning injector and the spinning receiving matrix is 15 cm-20 cm, the electric field intensity is 0.5 kV/cm-2 kV/cm, and the rotating speed of the spinning receiving matrix is 100rpm-500rpm, and forming the mixed precursor protofilament on the spinning receiving matrix;
and/or the ambient temperature of the electrostatic spinning is 20-30 ℃, and the relative humidity is 10-50%;
and/or the inner diameter of a needle head of a spinning injector used for electrostatic spinning is 0.8 mm-1.1 mm.
5. The method for preparing a metal monoatomic-supported composite material according to claim 4, wherein the pre-oxidation treatment includes: heating the precursor mixture to 200-300 ℃ in the air atmosphere with the heating rate of 0.5-5 ℃/min, and then preserving the heat for 1-5 h;
and/or the step of carbonizing comprises: and under the inert atmosphere with the heating rate of 0.5-5 ℃/min, heating the product after the pre-oxidation treatment to 800-1200 ℃, and then preserving the heat for 0.5-5 h.
6. The method for preparing a metal monoatomic-supported composite material according to claim 5, wherein the acid oxidation treatment step includes: according to the proportion of the mass of the carbonized product to the volume of the oxidizing acid solution of 1 mg: (1-10) mL, mixing the carbonized product with an oxidizing acid solution, reacting for 2-8 h at the temperature of 80-120 ℃, and separating and drying to obtain the composite material loaded with the metal monoatomic atoms.
7. The method of preparing a metal monatomic-loaded composite material according to claim 6, wherein the oxidizing acid solution is selected from the group consisting of: at least one of sulfuric acid, nitric acid and hydrochloric acid;
and/or the concentration of the oxidizing acid solution is 1-6 mol/L.
8. A metal monoatomic-supported composite material manufactured by the method according to any one of claims 1 to 7, wherein the metal monoatomic-supported composite material includes carbon nanofibers and nitrogen elements doped in the carbon nanofibers and metal monoatomic atoms supported on the carbon nanofibers.
9. The metal monatomic-loaded composite material of claim 8, wherein the metal monatomic loading is from 0.1 wt% to 20 wt%;
and/or the loading amount of the nitrogen element is 0.1-10 wt%;
and/or the diameter of the carbon nanofiber is 100-300 nm.
10. The application of the composite material loaded with metal monoatomic atoms is characterized in that the composite material loaded with metal monoatomic atoms prepared by the method as claimed in any one of claims 1 to 7 or the composite material loaded with metal monoatomic atoms as claimed in any one of claims 8 to 9 is applied to a fuel cell or hydrogen production by water electrolysis.
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