CN108906056A - A kind of preparation of inverse spinel structure Co ferrite Nano powder and electro-catalysis application with oxygen defect - Google Patents
A kind of preparation of inverse spinel structure Co ferrite Nano powder and electro-catalysis application with oxygen defect Download PDFInfo
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- CN108906056A CN108906056A CN201810683023.5A CN201810683023A CN108906056A CN 108906056 A CN108906056 A CN 108906056A CN 201810683023 A CN201810683023 A CN 201810683023A CN 108906056 A CN108906056 A CN 108906056A
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- nano powder
- oxygen defect
- ferrite nano
- cobalt
- electrode
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 99
- 239000001301 oxygen Substances 0.000 title claims abstract description 99
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 87
- 230000007547 defect Effects 0.000 title claims abstract description 84
- 239000011858 nanopowder Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 14
- 229910052596 spinel Inorganic materials 0.000 title claims description 28
- 239000011029 spinel Substances 0.000 title claims description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 235000013495 cobalt Nutrition 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 4
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 229910002588 FeOOH Inorganic materials 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 241000208340 Araliaceae Species 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- 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 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000002086 nanomaterial Substances 0.000 description 17
- 238000002484 cyclic voltammetry Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 235000019263 trisodium citrate Nutrition 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 238000001548 drop coating Methods 0.000 description 5
- 238000002847 impedance measurement Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229940068911 chloride hexahydrate Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical class O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- 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
Abstract
The present invention provides a kind of simple preparation method of Co ferrite Nano powder with oxygen defect and its electro-catalysis applications.Firstly, preparing alkaline ferro-cobalt aqueous solution, heating reaction obtains Co ferrite Nano powder；Then, obtained Conjugate ferrite is introduced by oxygen defect by room temperature reduction method, finally obtains the Co ferrite Nano powder with oxygen defect.Conjugate ferrite with oxygen defect is applied to electro-catalysis and produces oxygen reaction（OER）In have excellent catalytic properties, overpotential is reduced to 0.330 V（Relative standard's hydrogen electrode）, Tafel slope is down to 44 mV/dec.
Description
Technical field
The present invention relates to the preparation of inorganic nanometer powder and application fields, and in particular to one kind is had based on hydro-thermal method preparation
The method of the inverse spinel structure Co ferrite Nano powder of oxygen defect and application in electro-catalysis water decomposition.
Background technique
With dependence of the today's society to fossil energy gradually increase and its consumption process in bring environmental pollution ask
Topic is got worse, and exploration cleaning, efficient, reproducible new energy is extremely urgent.The Hydrogen Energy Yin Qigao in numerous new energies
The advantages that energy density, cleanliness without any pollution, recyclable regenerative, becomes the focus of research.Electrolysis water liberation of hydrogen is as safe and efficient
Production hydrogen approach cause the extensive concern of people.However, analysing oxygen half-reaction because of it is related to complicated four electronics courses electrolysis aquatic products
Hydrogen reaction receives very big limitation.So there is an urgent need to design the rate for synthesizing efficient catalyst to promote oxygen evolution reaction.
Report display at present, promoting the most effective catalyst of oxygen evolution reaction is noble metal Ir, Ru and its oxide, it is contemplated that noble metal valence
Lattice are expensive and content is rare limited on earth, limit its large-scale industrial production.Therefore, design is cheap, is easy to get, is high
The oxygen evolution reaction catalysts of effect are significant to the industrialized production of Hydrogen Energy.
Nano material is had been assigned due to its skin effect, quantum size effect, quantum tunneling effect, small-size effect etc.
Many special physicochemical properties.Each research field is made a general survey of, nano material has shown good application, electro-catalysis
It is no exception to decompose water field.CoFe2O4As a kind of transition metal oxide with inverse spinel structure, excellent is steady
It is qualitative to be aroused widespread concern in catalytic field.With further going deep into inverse spinel structure oxide properties
It probes into and the nano ZnO control measures of current development, CoFe2O4As inverse spinel oxide important member its
Application field will be widened significantly, and significant Social benefit and economic benefit is generated, or even be hopeful to realize the industry of Hydrogen Energy
Metaplasia produces.
Making a general survey of various regulations improves effective chemical means of catalytic performance, and manufacturing defect is a kind of novel, efficient, safety
Control measures, defect can be realized by reducing reaction energy barrier, creating the approach such as defect sites, raising electric conductivity to catalysis material
Optimising and adjustment.But the defect reported at present is largely focused on the pattern and crystal structure of material, is keeping assertive evidence lattice
The defect of specific atoms in material is realized while structure to promote catalytic performance faces enormous challenge.Xie Yi team report
Oxygen defect is manufactured in nickel cobalt oxysome ultrathin nanometer piece by air calcination method and is realized, nickel cobalt oxysome catalyst performance is optimized, and
And show that nickel cobalt oxysome catalyst can be greatly lowered to the adsorption energy of hydrone in oxygen defect by Density functional Modeling Calculation,
The final optimising and adjustment for realizing catalytic performance；Wang Shuanyin team report, through plasma etching method in sheet cobalt/cobalt oxide
It is successfully incorporated into oxygen defect, by manufacturing more defect sites, introducing defect level, successfully improves the catalysis of cobalt/cobalt oxide
Activity；Furthermore display is had been reported that in the recent period, and ultrasonic stripping method can also introduce Lacking oxygen in the material.But above-mentioned introducing oxygen is empty
These method complicated difficults operation of position, technical requirements height are unfavorable for universal on a large scale.In consideration of it, the present invention provides a kind of simple
The efficient method for introducing reducing agent is keeping CoFe2O4Assertive evidence crystal structure manufactures oxygen defect simultaneously, to significantly be promoted
CoFe2O4The strategy of nano-powder electrolysis aquatic products oxygen catalytic activity.
Summary of the invention
Present invention solves the problem in that providing a kind of inverse spinel structure Co ferrite Nano powder system with oxygen defect
Preparation Method and its electrocatalysis characteristic application.In order to solve the above problem the technical scheme is that：
1. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, includes the following steps：
（1）The aqueous solution that ferro-cobalt source is prepared first in reaction unit, ferro-cobalt source aqueous solution is pre-processed, and alkaline conditioner is added
Alkalescent iron cobalt source reaction solution is prepared, heats reaction solution, after a certain period of time, natural cooling is collected by centrifugation to obtain cobalt for reaction
Ferrite nano powder；（2）In aqueous solution by reducing agent ultrasonic disperse, ferro-cobalt nano-powder is added under mechanical stirring
In the reducing agent aqueous solution prepared, after a certain period of time, product washing, centrifugation, collection, vacuum drying are obtained with oxygen for reaction
The Co ferrite Nano powder of defect.
2. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（1）In, source of iron is Iron(III) chloride hexahydrate, FeOOH, six ferric sulfate hydrates, Iron dichloride tetrahydrate, nine nitric hydrates
One or more of iron, di-iron trioxide, ferroso-ferric oxide, ferric acetate, six ferric sulfate hydrate ammoniums, optimal is six hydration trichlorines
Change iron, Fe(NO3)39H2O, the concentration of molysite aqueous solution is 0.01 ~ 0.04 mol/L, and optimal is 0.02 ~ 0.03 mol/
L。
3. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（1）In, cobalt source is cobalt chloride hexahydrate, cobalt sesquioxide, cobaltosic oxide, cobaltous sulfate, nine nitric hydrate cobalts, cobalt acetate, cobalt
One or more of powder, acetylacetone cobalt, optimal is cobalt nitrate, cobalt chloride hexahydrate, and the concentration of cobalt saline solution is 0.005
~ 0.015 mol/L, optimal is 0.007 ~ 0.01 mol/L.
4. a kind of simple preparation method of the Co ferrite Nano powder with oxygen defect, the step（1）In, cobalt source
Molar ratio with source of iron is 1 ~ 3:3 ~ 9, optimal is 1: 3.
5. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（1）In, alkaline conditioner used is sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium citrate, cesium hydroxide, carbonic acid
One or more of sodium, potassium carbonate, cesium carbonate, sodium bicarbonate, saleratus, triethylamine, trimethylamine, 1,10-Phens
Combination, it is optimal be trisodium citrate, sodium carbonate.
6. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（1）In, alkaline conditioner adjusts ferro-cobalt source aqueous solution to PH=8 ~ 10, and optimal is to be adjusted to solution ph=8 ~ 9.
7. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（1）In, by gained alkalescent iron cobalt source aqueous solution 130 ~ 160oC insulation reaction 18 ~ 30 hours, optimal was 140 ~ 150oC insulation reaction 22 ~ 26 hours.
8. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（1）In, reaction unit is stainless steel cauldron, hydro-thermal autoclave.
9. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（2）In, the concentration of Conjugate ferrite is 0.002 ~ 0.01 mol/L.
10. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（2）In, reducing agent is sodium borohydride, in formaldehyde, tetrabutyl ammonium borohydride, trisodium citrate, hydrazine hydrate, ascorbic acid, oleic acid
One or more, optimal is sodium borohydride, hydrazine hydrate, and the concentration of reducing agent aqueous solution is 0.5 ~ 2 mol/L, and optimal is 1
~ 1.5 mol/L。
11. a kind of simple preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, the step
（2）In, resulting reaction solution is placed in 30 ~ 40oUnder C, mechanic whirl-nett reaction 1 ~ 6 hour, optimal was 3 ~ 5 small
When.
12. the simple preparation and its electro-catalysis of a kind of inverse spinel structure Co ferrite Nano powder with oxygen defect are answered
With, using three-electrode system, the oxygen performance test of electrocatalytic decomposition aquatic products is carried out on electrochemical workstation, it is scarce with oxygen to be coated with
The platinum carbon electrode of sunken Co ferrite Nano powder is working electrode, is to electrode, using Ag/AgCl electrode as reference with platinum electrode
Electrode；Using 1 mol/L potassium hydroxide solution as electrolyte；Using H-type glass electrolytic cell as electrolysis reaction device.
Specific embodiment mode
In order to further appreciate that the present invention, the preferred embodiment of the invention is described below with reference to embodiment, but should
Understand, these descriptions are only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, six trichloride hydrates ferrous iron is sequentially added under stirring
（0.3180 g, 1.6 mmol）, cobalt nitrate（0.1470 g, 0.6 mmol）, 1.8185 g sodium carbonate are then added and adjust reaction
Liquid pH value is 9.5.130 °C of 30 h of baking oven inside holding is placed it in after sealing water thermal high kettle.After natural cooling, use respectively
Black Co ferrite Nano powder is obtained after deionized water, ethyl alcohol centrifuge washing vacuum drying.
Second step：It takes 50 mL deionized waters to be added in 200 mL beakers, 85% hydrazine hydrate is sequentially added under stirring（6.0
ML, 100 mmol）, Co ferrite Nano powder（50 mg, 0.2 mmol）, 30oContinue to be stirred to react 2 hours under C, obtain black
Color has the Co ferrite Nano powder of oxygen defect.
Third step：Co ferrite Nano powder electrolysis water application with oxygen defect
1. weighing the Conjugate ferrite nanometer powder that 5 mg have oxygen defect, it is added to the in the mixed solvent of 1mL ethyl alcohol and water（Second
The volume ratio of alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 20 minutes obtains black clarification dispersion
Liquid.The 4 above-mentioned dispersion liquids of μ L are taken, for drop coating in platinum carbon electrode surface, platinum carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the platinum carbon electrode of the Co ferrite Nano powder with oxygen defect as working electrode, with platinum electrode be to electrode,
Ag/AgCl electrode is reference electrode.It is reaction dress with H-type glass electrolytic cell using 1 mol/L potassium hydroxide solution as electrolyte
It sets.
3. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, in three electrode bodies
Cyclic voltammetry is carried out in system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V, maximum potential 0.8
V, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.Sampling interval is
0.001 V, time of repose are 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the platinum carbon electrode of the Conjugate ferrite nano material with oxygen defect as work
Make electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0 V,
Termination current potential is 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, to catalyst into
Row ac impedance measurement, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V, high frequency 100000
Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, the cobalt with oxygen defect
Ferrite has excellent effect in being applied to OER, and the overpotential that catalysis water electrolysis produces oxygen is 0.339 V（Relative standard's hydrogen electricity
Pole）, Tafel slope is 49 mV/dec.
Embodiment 2
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, is added with stirring di-iron trioxide（0.0639 g, 0.4
mmol）, acetylacetone cobalt（0.0715 g, 0.2 mmol）, 0.5351 g sodium hydroxide adjusting reacting liquid pH value is added afterwards is
8.5.160 °C of 30 h of baking oven inside holding is placed it in after sealing water thermal high kettle.After natural cooling, respectively with deionized water,
Black Co ferrite Nano powder is obtained after ethyl alcohol centrifuge washing vacuum drying.
Second step：It takes 50 mL deionized waters to be added in 200 mL beakers, sequentially adds tetrabutyl ammonium borohydride under stirring
（6.4327 g, 25 mmol）, Co ferrite Nano powder（25 mg, 0.1 mmol）, 35oContinue to be stirred to react 6 hours under C,
Obtain the Co ferrite Nano powder that black has oxygen defect.
Third step：Co ferrite Nano powder electrolysis water application with oxygen defect
1. weighing the Conjugate ferrite nanometer powder that 5 mg have oxygen defect, it is added to the in the mixed solvent of 1mL ethyl alcohol and water（Second
The volume ratio of alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 20 minutes obtains black clarification dispersion
Liquid.The 4 above-mentioned dispersion liquids of μ L are taken, for drop coating in platinum carbon electrode surface, platinum carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the platinum carbon electrode of the Co ferrite Nano powder with oxygen defect as working electrode, with platinum electrode be to electrode,
Ag/AgCl electrode is reference electrode.It is reaction dress with H-type glass electrolytic cell using 1 mol/L potassium hydroxide solution as electrolyte
It sets.
3. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, in three electrode bodies
Cyclic voltammetry is carried out in system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V, maximum potential 0.8
V, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.Sampling interval is
0.001 V, time of repose are 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the platinum carbon electrode of the Conjugate ferrite nano material with oxygen defect as work
Make electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0 V,
Termination current potential is 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, to catalyst into
Row ac impedance measurement, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V, high frequency 100000
Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, the cobalt with oxygen defect
Ferrite has excellent effect in being applied to OER, and the overpotential that catalysis water electrolysis produces oxygen is 0.336 V（Relative standard's hydrogen electricity
Pole）, Tafel slope is 50 mV/dec.
Embodiment 3
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, is added with stirring ferric chloride hexahydrate（0.2162 g,
0.8 mmol）, cobalt nitrate（0.0735 g, 0.3 mmol）, 0.9351 g trisodium citrate adjusting reacting liquid pH value is added afterwards is
8.0.140 °C of 26 h of baking oven inside holding is placed it in after sealing water thermal high kettle.After natural cooling, respectively with deionized water,
Black Co ferrite Nano powder is obtained after ethyl alcohol centrifuge washing vacuum drying.
Second step：It takes 50 mL deionized waters to be added in 200 mL beakers, sequentially adds sodium borohydride under stirring
（1.8901 g, 50 mmol）, Co ferrite Nano powder（50 mg, 0.2 mmol）, 40oContinue to be stirred to react 4 hours under C,
Obtain the Co ferrite Nano powder that black has oxygen defect.
Third step：Co ferrite Nano powder electrolysis water application with oxygen defect
1. weighing the Conjugate ferrite nanometer powder that 5 mg have oxygen defect, it is added to the in the mixed solvent of 1mL ethyl alcohol and water（Second
The volume ratio of alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 20 minutes obtains black clarification dispersion
Liquid.The 4 above-mentioned dispersion liquids of μ L are taken, for drop coating in platinum carbon electrode surface, platinum carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the platinum carbon electrode of the Co ferrite Nano powder with oxygen defect as working electrode, with platinum electrode be to electrode,
Ag/AgCl electrode is reference electrode.It is reaction dress with H-type glass electrolytic cell using 1 mol/L potassium hydroxide solution as electrolyte
It sets.
3. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, in three electrode bodies
Cyclic voltammetry is carried out in system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V, maximum potential 0.8
V, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.Sampling interval is
0.001 V, time of repose are 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the platinum carbon electrode of the Conjugate ferrite nano material with oxygen defect as work
Make electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0 V,
Termination current potential is 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, to catalyst into
Row ac impedance measurement, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V, high frequency 100000
Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, the cobalt with oxygen defect
Ferrite has excellent effect in being applied to OER, and the overpotential that catalysis water electrolysis produces oxygen is 0.330 V（Relative standard's hydrogen electricity
Pole）, Tafel slope is 45 mV/dec.
Embodiment 4
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, is added with stirring Fe(NO3)39H2O（0.2901 g,
1.2 mmol）, cobalt chloride hexahydrate（0.0951 g, 0.4 mmol）, rear that 2.1836 g trisodium citrates adjusting reaction solution is added
PH value is 9.0.150 °C of 24 h of baking oven inside holding is placed it in after sealing water thermal high kettle.After natural cooling, spend respectively
Black Co ferrite Nano powder is obtained after ionized water, ethyl alcohol centrifuge washing vacuum drying.
Second step：It takes 50 mL deionized waters to be added in 200 mL beakers, 85% hydrazine hydrate is sequentially added under stirring（4.5
ML, 75 mmol）, Co ferrite Nano powder（100 mg, 0.4 mmol）, 40oContinue to be stirred to react 5 hours under C, obtain black
Color has the Co ferrite Nano powder of oxygen defect.
Third step：Co ferrite Nano powder electrolysis water application with oxygen defect
1. weighing the Conjugate ferrite nanometer powder that 5 mg have oxygen defect, it is added to the in the mixed solvent of 1mL ethyl alcohol and water（Second
The volume ratio of alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 20 minutes obtains black clarification dispersion
Liquid.The 4 above-mentioned dispersion liquids of μ L are taken, for drop coating in platinum carbon electrode surface, platinum carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the platinum carbon electrode of the Co ferrite Nano powder with oxygen defect as working electrode, with platinum electrode be to electrode,
Ag/AgCl electrode is reference electrode.It is reaction dress with H-type glass electrolytic cell using 1 mol/L potassium hydroxide solution as electrolyte
It sets.
3. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, in three electrode bodies
Cyclic voltammetry is carried out in system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V, maximum potential 0.8
V, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.Sampling interval is
0.001 V, time of repose are 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the platinum carbon electrode of the Conjugate ferrite nano material with oxygen defect as work
Make electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0 V,
Termination current potential is 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, to catalyst into
Row ac impedance measurement, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V, high frequency 100000
Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, the cobalt with oxygen defect
Ferrite has excellent effect in being applied to OER, and the overpotential that catalysis water electrolysis produces oxygen is 0.330 V（Relative standard's hydrogen electricity
Pole）, Tafel slope is 44 mV/dec.
Embodiment 5
The first step：50 mL hydrothermal reaction kettle of use for laboratory is taken, hydrothermal reaction kettle has stainless steel casing, polytetrafluoroethylliner liner.
It takes 40 mL deionized waters to be added in 50 mL polytetrafluoroethylliner liners, is added with stirring Fe(NO3)39H2O（0.2177 g,
0.9 mmol）, cobalt nitrate（0.0735 g, 0.3 mmol）, 1.4962 g trisodium citrates adjusting reacting liquid pH value is added afterwards is
8.5.145 °C of 25 h of baking oven inside holding is placed it in after sealing water thermal high kettle.After natural cooling, respectively with deionized water,
Black Co ferrite Nano powder is obtained after ethyl alcohol centrifuge washing vacuum drying.
Second step：It takes 50 mL deionized waters to be added in 200 mL beakers, sequentially adds sodium borohydride under stirring
（1.8910 50 mmol）, Co ferrite Nano powder（75 mg, 0.3 mmol）, 30oContinue to be stirred to react 3 hours under C, obtain
There is the Co ferrite Nano powder of oxygen defect to black.
Third step：Co ferrite Nano powder electrolysis water application with oxygen defect
1. weighing the Conjugate ferrite nanometer powder that 5 mg have oxygen defect, it is added to the in the mixed solvent of 1mL ethyl alcohol and water（Second
The volume ratio of alcohol and water is 3: 7）, while 50 μ L Nafion solutions are added, ultrasound 20 minutes obtains black clarification dispersion
Liquid.The 4 above-mentioned dispersion liquids of μ L are taken, for drop coating in platinum carbon electrode surface, platinum carbon electrode diameter is 3 mm, naturally dry.
2. using three-electrode system, electrocatalytic decomposition aquatic products oxygen performance is carried out on occasion China 660E electrochemical workstation and is surveyed
Examination.To be coated with the platinum carbon electrode of the Co ferrite Nano powder with oxygen defect as working electrode, with platinum electrode be to electrode,
Ag/AgCl electrode is reference electrode.It is reaction dress with H-type glass electrolytic cell using 1 mol/L potassium hydroxide solution as electrolyte
It sets.
3. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, in three electrode bodies
Cyclic voltammetry is carried out in system, activates sample.Cyclic voltammetry voltage range is 0 ~ 0.8 V, maximum potential 0.8
V, 0 V of potential minimum, beginning current potential are 0 V, and termination current potential is 0.8 V.Sweep speed is 0.05 V/s.Sampling interval is
0.001 V, time of repose are 2 s, and scanning number of segment is 500.
4. after cyclic voltammetry, to be coated with the platinum carbon electrode of the Conjugate ferrite nano material with oxygen defect as work
Make electrode, linear voltage sweep test is carried out in three-electrode system, voltage range is 0 ~ 0.8 V.Initial potential is 0 V,
Termination current potential is 0.8 V.Sweep speed is 5 mV/s.Sampling interval is 0.001 V.Time of repose is 2 s.
5. using the platinum carbon electrode for being coated with the Conjugate ferrite nano material with oxygen defect as working electrode, to catalyst into
Row ac impedance measurement, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is 0.6 V, high frequency 100000
Hz, low frequency 0.1Hz.Amplitude is 0.005 V, and quiescent time is 2 s.After data processing and calculating, the cobalt with oxygen defect
Ferrite has excellent effect in being applied to OER, and the overpotential that catalysis water electrolysis produces oxygen is 0.334 V（Relative standard's hydrogen electricity
Pole）, Tafel slope is 46 mV/dec.
Claims (9)
1. a kind of preparation method of the inverse spinel structure Co ferrite Nano powder with oxygen defect, which is characterized in that preparation step
It is rapid as follows：（1）Ferro-cobalt source aqueous solution is prepared in reaction unit, and alkaline conditioner is added and prepares basic iron cobalt source aqueous solution, adds
After a certain period of time, natural cooling, centrifugation, washing are collected obtains Co ferrite Nano powder to thermal response；（2）By reducing agent ultrasound point
It dissipates in deionized water, Co ferrite Nano powder is added in the reducing agent aqueous solution prepared carries out under mechanical stirring
Oxygen defect reaction is introduced, product washing, centrifugation, collection, vacuum drying are obtained into the inverse spinel structure ferro-cobalt oxygen with oxygen defect
Body nano-powder.
2. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（1）In, source of iron is Iron(III) chloride hexahydrate, FeOOH, six ferric sulfate hydrates, four water
Close frerrous chloride, Fe(NO3)39H2O, di-iron trioxide, ferroso-ferric oxide, ferric acetate, one of six ferric sulfate hydrate ammoniums or
Several, the concentration of source of iron aqueous solution is 0.01 ~ 0.04 mol/L.
3. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（1）In, cobalt source be cobalt chloride hexahydrate, cobalt sesquioxide, cobaltosic oxide, cobaltous sulfate,
One or more of nine nitric hydrate cobalts, cobalt acetate, cobalt powder, acetylacetone cobalt, the concentration of cobalt saline solution is 0.005 ~
0.015 mol/L。
4. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（1）In, the molar ratio of cobalt source and source of iron is 1 ~ 3: 3 ~ 9.
5. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（1）In, alkaline conditioner used is sodium hydroxide, potassium hydroxide, lithium hydroxide, lemon
Sour trisodium, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, saleratus, triethylamine, trimethylamine, 1,10-neighbours
The combination of one or more of phenanthroline, alkaline conditioner adjust ferro-cobalt source aqueous solution to PH=8 ~ 10.
6. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（1）In, by gained basic iron cobalt source aqueous solution 130 ~ 160oReaction is heated under C, instead
It answers 18 ~ 30 hours.
7. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（2）In, reducing agent be sodium borohydride, formaldehyde, tetrabutyl ammonium borohydride, trisodium citrate,
One or more of hydrazine hydrate, ascorbic acid, oleic acid, the concentration of reducing agent aqueous solution are 0.5 ~ 2 mol/L.
8. a kind of preparation side of inverse spinel structure Co ferrite Nano powder with oxygen defect according to claim 1
Method, which is characterized in that the step（2）In, resulting reaction solution is placed in 30 ~ 40oIt is reacted under C, mechanical stirring 1 ~
6 hours.
9. the simple preparation and electro-catalysis application of a kind of inverse spinel structure Co ferrite Nano powder with oxygen defect, feature
It is, using three-electrode system, carries out the oxygen performance test of electrocatalytic decomposition aquatic products, on electrochemical workstation to be coated with oxygen
The platinum carbon electrode of the Co ferrite Nano powder of defect is working electrode, is to electrode with platinum electrode, is ginseng with Ag/AgCl electrode
Compare electrode；Using 1 mol/L potassium hydroxide solution as electrolyte；Using H-type glass electrolytic cell as electrolysis reaction device.
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| CN113853356A (en) * | 2019-05-24 | 2021-12-28 | 日铁矿业株式会社 | Method for producing cobalt ferrite particles and cobalt ferrite particles produced thereby |
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| CN111729672A (en) * | 2019-12-11 | 2020-10-02 | 中国科学院深圳先进技术研究院 | Fully decomposed water surface modified molybdenum dioxide catalyst and preparation method and application thereof |
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| CN113501547B (en) * | 2021-07-05 | 2022-08-30 | 南京工业大学 | Preparation method of nitrogen-doped graphene-loaded inverse spinel type magnetic aerogel material |
| WO2022233340A1 (en) * | 2021-09-16 | 2022-11-10 | 中国科学院大学 | Vocs combustion catalyst prepared from recycled waste ternary lithium-ion batteries, and preparation method therefor |
| CN114235918A (en) * | 2021-12-09 | 2022-03-25 | 广西壮族自治区农业科学院 | Method for detecting carbendazim by adopting intrinsic defect porous carbon material |
| CN114235918B (en) * | 2021-12-09 | 2023-10-31 | 广西壮族自治区农业科学院 | Method for detecting carbendazim by adopting intrinsic defect porous carbon material |
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