CN115611324A - Nickel-cobalt bimetal-based submicron flower cluster and preparation method and application thereof - Google Patents
Nickel-cobalt bimetal-based submicron flower cluster and preparation method and application thereof Download PDFInfo
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- CN115611324A CN115611324A CN202211356891.5A CN202211356891A CN115611324A CN 115611324 A CN115611324 A CN 115611324A CN 202211356891 A CN202211356891 A CN 202211356891A CN 115611324 A CN115611324 A CN 115611324A
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- nickel
- cobalt
- submicron
- flower
- hydroxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 27
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 27
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims abstract description 13
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- IJUKXQRCJABGNO-UHFFFAOYSA-N [Se].[Ni]=[Se] Chemical compound [Se].[Ni]=[Se] IJUKXQRCJABGNO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 11
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims abstract description 11
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 4
- -1 nickel cobalt glycerate Chemical compound 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000011144 upstream manufacturing Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 38
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 24
- 230000010287 polarization Effects 0.000 description 23
- 238000001228 spectrum Methods 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 238000006460 hydrolysis reaction Methods 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 12
- 239000002135 nanosheet Substances 0.000 description 12
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 11
- 102000020897 Formins Human genes 0.000 description 8
- 108091022623 Formins Proteins 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- 229910002441 CoNi Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- 239000004480 active ingredient Substances 0.000 description 1
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- 230000002238 attenuated effect Effects 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 238000003892 spreading Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- 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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P2004/00—Particle morphology
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a nickel-cobalt bimetallic-based submicron flower cluster, which is a nickel hydroxide/cobalt hydroxide submicron flower cluster with the diameter of 500-650 nm and formed by preparing a plurality of nanometer flower petals with the thickness of 2-30 nm by using nickel hydroxide/cobalt hydroxide as components, wherein the content of nickel and cobalt is 1: (1-4) or (1-4): 1; and the nickel hydroxide/cobalt hydroxide submicron flower clusters are used as substrates to respectively prepare nickelous phosphide/cobaltous phosphide submicron flower clusters or nickel disulfide/cobalt disulfide submicron flower clusters or nickel diselenide/cobalt diselenide submicron flower clusters or nickel oxide/cobalt oxide submicron flower clusters. The submicron flower cluster has the highest hydrogen evolution catalytic activity in an alkaline medium, gets rid of the limitation of conductive matrix components, has good durability, can be used as a hydrogen evolution reaction electrocatalyst, and is suitable for industrial production. The invention also discloses a preparation method of the nickel-cobalt bimetallic-based submicron flower cluster.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis materials, and particularly relates to a nickel-cobalt bimetal-based submicron flower cluster, and a preparation method and application thereof.
Background
The hydrogen production by electrolyzing water is a high-efficiency, reliable, safe and environment-friendly hydrogen production method. The key steps involved in the process of electrolysis of water include cathodic Hydrogen Evolution Reaction (HER) and anodic Oxygen Evolution Reaction (OER), with a theoretical value of decomposition voltage of 1.23V. But because of the slow kinetics of the hydrogen evolution and oxygen evolution reactions, the overpotential is high, the actual decomposition voltage is far higher than 1.23V, and the energy consumption for producing hydrogen by electrolyzing water is increased. Therefore, the design of the oxygen evolution reaction and hydrogen evolution reaction electrocatalyst with high electrocatalytic activity and high stability reduces the overpotential of the cathode and anode reactions, and has important significance for improving the energy conversion and hydrogen production efficiency.
In order to get rid of the limitations of high cost and low stability of noble metal catalysts, various non-noble metal catalysts have been studied. Among them, nickel-based and cobalt-based compounds have been demonstrated to have excellent HER electrocatalytic activity, such as nickel cobalt hydroxide, phosphide, sulfide, selenide, and the like. In order to improve the utilization rate of active ingredients, the compounds are often supported on the surface of a carbon matrix in the form of nano particles, but the compounds are easy to fall off during the operation of the composite material, so that the stability of the catalyst is influenced. The compound is prepared into a submicron flower cluster structure consisting of nanosheets, so that active sites can be greatly increased, the electron and charge transmission efficiency and stability can be improved, the limit of a conductive substrate can be even eliminated, and the compound can be directly used for electrocatalysis. Wang et al by electrodepositionMethod for growing CoNi on nickel skeleton 2 S 4 Petal-like structures (j. Mater. Chem.a,2015,3, 23035-23041); rezaee et al grown metal organic framework material on carbon substrate, followed by subsequent processing to obtain Ni x Co 2-x P nanocrystallized/C composite material (Nanoscale, 2020,12, 16123-16135). However, none of these methods is free from the limitation of the conductive base component and is applicable only to a limited compound system. Therefore, a simple and universal method for preparing the nickel-cobalt bimetallic-based submicron flower cluster without being limited by a conductive matrix is not available at present.
Disclosure of Invention
The invention aims to overcome the problems and defects of the prior art and provides a nickel-cobalt bimetallic-based submicron flower cluster and a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by adopting the following scheme.
The nickel-cobalt bimetal-based submicron flower cluster is characterized in that the nickel hydroxide/cobalt hydroxide submicron flower cluster with the diameter of 500-650 nm is formed by preparing a plurality of nanometer flower petals with the thickness of 2-30 nm by using nickel hydroxide/cobalt hydroxide as components, wherein the content of nickel and cobalt is 1: (1-4) or (1-4): 1; and the nickel hydroxide/cobalt hydroxide submicron flower cluster is used as a substrate to prepare a nickelous phosphide/cobaltous phosphide submicron flower cluster or a nickel disulfide/cobalt disulfide submicron flower cluster or a nickel diselenide/cobalt diselenide submicron flower cluster or a nickel oxide/cobalt oxide submicron flower cluster.
In order to achieve the above purpose, the present invention is realized by adopting another technical scheme as follows.
A preparation method of a nickel-cobalt bimetal-based submicron flower cluster specifically comprises the following steps:
(1) Preparation of nickel cobalt glycerate submicron sphere precursor
Nickel salt according to mass/volume ratio: isopropyl alcohol = (0.5 to 2): 1mg/mL and cobalt salt: isopropyl alcohol = (0.5 to 2): 1mg/mL, dissolving nickel salt and cobalt salt in isopropanol to obtain a nickel-cobalt salt solution; glycerol in volume ratio: the nickel cobalt salt solution is 1: (3-7) adding glycerol, performing ultrasonic treatment for 10-20 min, transferring the mixture into a hydrothermal reaction kettle, and keeping the temperature at 150-200 ℃ for 15-20 h; washing with absolute ethyl alcohol, and drying at 40-80 ℃ for 5-10 h to obtain nickel-cobalt glycerate submicron spheres;
(2) Preparation of nickel hydroxide/cobalt hydroxide submicron flower cluster
The method comprises the following steps of (1) preparing nickel cobalt glycerate submicron spheres according to mass/volume ratio: deionized water = (0.5 to 5): 1mg/mL, dispersing the nickel cobalt glycerate submicron spheres obtained in the step (1) in deionized water, carrying out ultrasonic treatment for 15-30 min, transferring the dispersion liquid into a hydrothermal reaction kettle, and carrying out heat preservation at 150-200 ℃ for 5-9 h to hydrolyze the nickel cobalt glycerate submicron spheres and convert the nickel cobalt glycerate submicron spheres into nickel hydroxide/cobalt hydroxide submicron clusters;
(3) Preparation of nickelous phosphide/cobaltous phosphide or nickel disulfide/cobaltous disulfide or nickel diselenide/cobaltous diselenide or nickel oxide/cobalt oxide submicron flower cluster
(3-1) mixing the nickel hydroxide/cobalt hydroxide submicron flower cluster obtained in the step (2) and a phosphorus source according to a mass ratio of 1: (10-15) respectively placing the ceramic boats at the downstream and the upstream, placing the ceramic boats in a tubular furnace, calcining the ceramic boats to 300-500 ℃ in an inert atmosphere, preserving the heat for 90-180 min, and cooling to obtain the nickelous phosphide/cobaltous phosphide submicron flower clusters;
(3-2) mixing the nickel hydroxide/cobalt hydroxide submicron flower cluster obtained in the step (2) and sublimed sulfur according to the mass ratio of 1: (2-5) respectively placing the ceramic boat at the downstream and the upstream, placing the ceramic boat in a tube furnace, calcining the ceramic boat in an inert atmosphere to 300-500 ℃, preserving the heat for 90-180 min, and cooling to obtain a nickel disulfide/cobalt disulfide submicron flower cluster;
(3-3) mixing the nickel hydroxide/cobalt hydroxide submicron flower clusters obtained in the step (2) and selenium powder according to a mass ratio of 1: (3-7) respectively placing the ceramic boat at the downstream and the upstream, placing the ceramic boat in a tube furnace, calcining the ceramic boat to 300-500 ℃ in an inert atmosphere, preserving the heat for 90-180 min, and cooling to obtain the nickel diselenide/cobalt diselenide submicron flower clusters;
and (3-4) calcining the nickel hydroxide/cobalt hydroxide submicron flower cluster obtained in the step (2) in air to 300-500 ℃, preserving the temperature for 90-180 min, and cooling to obtain the nickel oxide/cobalt oxide submicron flower cluster.
Further preferably, the nickel salt in step (1) is nickel nitrate, nickel acetate or nickel chloride.
Further preferably, the cobalt salt in step (1) is cobalt nitrate, cobalt acetate or cobalt chloride.
Further preferably, the phosphorus source in step (3) is sodium hypophosphite or red phosphorus.
Further preferably, the temperature rising rate of the calcination in the inert atmosphere to 300-500 ℃ in the step (3) is 1-5 ℃/min.
Further preferably, the inert atmosphere in step (3) is nitrogen or argon.
Further preferably, the temperature rise rate of the calcination in air to 300-500 ℃ in the step (3) is 1-5 ℃/min.
The invention relates to an application of a nickel-cobalt bimetal-based submicron flower cluster as a hydrogen evolution reaction electrocatalyst.
The invention has the advantages and beneficial effects that:
the invention utilizes a hydrothermal-hydrolysis method to prepare the nickel hydroxide/cobalt hydroxide submicron flower cluster, and then the nickel phosphide/cobaltous phosphide or nickel disulfide/cobalt disulfide or nickel diselenide/cobalt diselenide or nickel oxide/cobalt oxide submicron flower cluster is successfully obtained through topological transformation. Research shows that the nickelous phosphide/cobaltous phosphide submicron flower cluster has the highest hydrogen evolution catalytic activity in an alkaline medium, gets rid of the limitation of conductive matrix components, and can reach 10mA cm only by 153mV of overpotential -2 The current density of the copper alloy is high, the durability is good, and the copper alloy is suitable for industrial production.
Drawings
FIG. 1 shows Ni (OH) in example 1 2 /Co(OH) 2 XRD spectrum of (a).
FIG. 2 shows Ni (OH) in example 1 2 /Co(OH) 2 FESEM image (a) and TEM image (b) of (a).
FIG. 3 shows Ni (OH) prepared in example 1 2 /Co(OH) 2 And commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 The polarization curves are all corrected by iR compensation.
FIG. 4 shows Ni in example 2 2 P/Co 2 XRD spectrum of P.
FIG. 5 shows Ni in example 2 2 P/Co 2 FESEM image (a) and high power FESEM image (b) of P.
FIG. 6 shows Ni in example 2 2 P/Co 2 HRTEM image (a) and high resolution lattice image (b) of P.
FIG. 7 shows Ni in example 2 2 P/Co 2 XPS survey of P (a), ni 2P high-resolution survey (b), co 2P high-resolution survey (c), and P2P high-resolution survey (d).
FIG. 8 shows Ni prepared in example 2 2 P/Co 2 P and commercial Pt/C in N 2 1mol L of saturation -1 Polarization curve in KOH electrolyte, scan rate 2mV s -1 The polarization curves are all corrected by iR compensation.
FIG. 9 shows Ni prepared in example 2 2 P/Co 2 Current-time curves (a) and polarization curves (b) before and after 50h test for P at-166 mV (vs. RHE), -186mV (vs. RHE) and-216 mV (vs. RHE), respectively.
FIG. 10 shows NiS in example 3 2 /CoS 2 XRD spectrum of (1).
FIG. 11 shows NiS in example 3 2 /CoS 2 FESEM image (a) and high power FESEM image (b).
FIG. 12 is NiS prepared in example 3 2 /CoS 2 And commercial Pt/C in N 2 1mol L of saturation -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 The polarization curves are all corrected by iR compensation.
FIG. 13 shows NiSe in example 4 2 /CoSe 2 XRD spectrum of (a).
FIG. 14 shows NiSe in example 4 2 /CoSe 2 The FESEM image (a) and the high power FESEM image (b) of (a).
FIG. 15 is NiSe prepared in example 4 2 /CoSe 2 And commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 The polarization curves are all corrected by iR compensation.
FIG. 16 is the XRD spectrum of NiO/CoO in example 5.
FIG. 17 shows FESEM image (a) and high power FESEM image (b) of NiO/CoO in example 5.
FIG. 18 shows NiO/CoO and commercial Pt/C in N prepared in example 5 2 1mol L of saturation -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 The polarization curves are all corrected by iR compensation.
FIG. 19 is Ni (OH) prepared in example 6 with hydrolysis time of 5h 2 /Co(OH) 2 XRD spectrum of (1).
FIG. 20 shows Ni (OH) prepared in example 6 with a hydrolysis time of 5h 2 /Co(OH) 2 FESEM image of (a).
FIG. 21 is Ni (OH) having a hydrolysis time of 9h prepared in example 7 2 /Co(OH) 2 XRD spectrum of (a).
FIG. 22 shows Ni (OH) prepared in example 7 with a hydrolysis time of 9h 2 /Co(OH) 2 FESEM image of (a).
FIG. 23 shows Ni obtained in example 8 with a hydrolysis time of 5h 2 P/Co 2 XRD spectrum of P.
FIG. 24 shows Ni obtained in example 8 with a hydrolysis time of 5h 2 P/Co 2 FESEM image of P.
FIG. 25 shows Ni obtained in example 8 with a hydrolysis time of 5h 2 P/Co 2 P and commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 The polarization curves are all corrected by iR compensation.
FIG. 26 is Ni obtained by hydrolyzing for 9h in example 9 2 P/Co 2 XRD spectrum of P.
FIG. 27 shows Ni obtained in example 9 with a hydrolysis time of 9h 2 P/Co 2 FESEM image of P.
FIG. 28 shows Ni obtained in example 9 with a hydrolysis time of 9h 2 P/Co 2 P and commercial Pt/C in N 2 1mol L of saturation -1 Polarization curve in KOH electrolyte, scan rate 2mV s -1 The polarization curves are all corrected by iR compensation.
Detailed Description
In order that the nature of the invention may be better understood, reference will now be made to the following examples which are intended to illustrate the invention.
Example 1:
preparation, characterization and performance test of nickel hydroxide/cobalt hydroxide submicron flower cluster
(1) 58mg of Ni (NO) 3 ) 2 ·6H 2 O and 55mg Co (NO) 3 ) 2 ·9H 2 Adding 40mL of isopropanol into the O, and stirring until the isopropanol is completely dissolved to obtain a nickel-cobalt salt isopropanol solution; then 8mL of glycerol solution is measured and added into the nickel-cobalt salt isopropanol solution dropwise while stirring, ultrasonic treatment is carried out for 15min, then the mixture is transferred into a 70mL high-pressure reaction kettle and placed in an oven, and the temperature is kept at 180 ℃ for 16h. And cooling to room temperature, washing the precipitate with absolute ethyl alcohol for three times, and drying at 60 ℃ for 8 hours to obtain the nickel-cobalt glycerate submicron spheres.
(2) And dispersing 30mg of nickel cobalt glycerate submicron nanospheres into 30mL of deionized water, and performing ultrasonic treatment for 20min to obtain a uniform dispersion liquid. Transferring the dispersion liquid to a 50mL hydrothermal reaction kettle, placing the reaction kettle in an oven at 160 ℃, and keeping for 7 hours to hydrolyze the nickel cobalt glycerate submicron spheres into hydroxide.
FIG. 1 shows prepared Ni (OH) 2 /Co(OH) 2 XRD spectrum of (a). As can be seen from figure 1, the XRD spectrogram shows cliff type rise at about 34 degrees, which proves that the materials have ultra-thin structural characteristics, and the sharp diffraction peaks at 25 degrees and 60 degrees prove that the materials have better crystallinity. As can be seen from the FESEM image shown in FIG. 2 (a), ni (OH) 2 /Co(OH) 2 The nano-sheet is microscopically a three-dimensional flower cluster structure formed by orderly stacking two-dimensional nano-sheets, and the thickness of the nano-sheets is about 15nm. FIG. 2 (b) shows Ni (OH) 2 /Co(OH) 2 According to the TEM image, a nano flower cluster structure obtained by hydrolysis can be observed, and the nano flower cluster structure is assembled by two-dimensional nano sheets rich in wrinkles.
In order to further research the electrocatalytic performance of the material on hydrogen evolution reaction, a three-electrode system is adopted to carry out electrochemical performance test, and the obtained Ni (OH) 2 /Co(OH) 2 Graphite rod for counter electrode and electrode supported on glassy carbon electrode as working electrodeThe specific electrode is a mercury/mercury oxide electrode, and the electrolyte is 1mol L -1 Electrochemical tests were performed in aqueous KOH. FIG. 3 shows Ni (OH) 2 /Co(OH) 2 And commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve of electrochemical test performed in KOH solution, scan rate 2mV s -1 And the curve IR is corrected, ni (OH) can be seen from the figure 2 /Co(OH) 2 At 10mA cm -2 The overpotential under the current density is 392mV, which is 362mV higher than that of commercial Pt/C, and the HER catalytic performance is lower.
Example 2:
preparation, characterization and performance test of nickelous phosphide/cobaltous phosphide submicron flower cluster
The Ni (OH) obtained in example 1 was added 2 /Co(OH) 2 The material and sodium hypophosphite are respectively arranged at the downstream and the upstream of the porcelain boat according to the mass ratio of 1. Under argon atmosphere at 2 deg.C for min -1 The temperature rising rate is increased to 350 ℃, the temperature is kept for 2 hours at 350 ℃, and the mixture is naturally cooled to the room temperature to obtain the bimetallic phosphide Ni 2 P/Co 2 And P material. FIG. 4 is an XRD spectrum of the prepared material, with diffraction peaks 2 theta =44.6 °, 47.3 °, 54.2 ° and 74.7 ° with Ni 2 The (201), (210), (300) and (400) crystal planes of the P standard card (PDF # 03-0953) correspond to the diffraction peaks 2 θ =40.7 °, 41.0 ° and 43.3 ° of Co 2 The crystal faces of (121), (201) and (211) of the P standard card (PDF # 32-0306) correspond to each other, so that the prepared material is Ni 2 P phase and Co 2 And (4) P phase. Ni obtained from FIGS. 5 (a) and (b) 2 P/Co 2 The low power and high power FESEM images of the P sample can show that the thickness of the two-dimensional nano-sheet of the material is about 25nm, and the diameter of the flower cluster is about 600nm.
FIG. 6 (a) is a high-magnification TEM image in which Ni can be more clearly seen 2 P/Co 2 The surface of the nano sheet of the P material is provided with rich and fine nano particles, and Ni can be seen after further amplification 2 P and Co 2 The lattice of P. Wherein the 0.216 and 0.329nm stripe pitches shown in FIG. 6 (b) correspond to Co 2 The spacing of the (220) and (020) planes of P, and the 0.225nm fringe spacing corresponds to Ni 2 The pitch of the (111) plane of P.
FIG. 7 (a) is Ni prepared 2 P/Co 2 XPS full spectrum of P shows that C, O, P and Co elements exist in the sample. FIG. 7 (b) is an XPS high resolution spectrum of Ni 2p, which can be well fitted to four spin orbit peaks and two satellite peaks (sat.), where the signal peaks at 853.0eV and 856.4eV are assigned to Ni 2p 3/2 (ii) a The spike at 853.0eV indicates the formation of Ni-P species. The signal peaks at 870.5eV and 874.5eV are assigned to Ni 2p 1/2 In orbit, two satellite peaks associated at 786.5eV and 803.4eV, these signals demonstrate Ni 2+ Is present. FIG. 7 (c) shows XPS high resolution spectra of Co 2p, which can be classified as Co 2p 3/2 And Co 2p 1/2 Two, the main peaks observed at 778.2eV and 781.3eV are attributed to Co 2p 3/2 The sub-peak at 785.8eV is the satellite peak; and Co 2p 1/2 The main peaks at 792.9eV and 797.3eV, and the satellite peaks at 802.7eV associated therewith, prove that Co 2+ Is present. FIG. 7 (d) is an XPS high resolution spectrum of P2P, with a broad peak at high binding energy 134.1eV corresponding to the P-O bond, probably due to adsorption of oxygen in air at the surface of the material, and the fitted peaks at 129.4eV and 130.3eV respectively belong to P2P 3/2 And P2P 1/2 The peak at the lower binding energy of 129.4eV is derived from metal phosphide.
FIG. 8 shows Ni prepared 2 P/Co 2 P and commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 And corrected by iR compensation, ni is shown in the figure 2 P/Co 2 P is at 10mA cm -2 The overpotential at current density was 0.153V, only 123mV higher than commercial Pt/C, exhibiting excellent HER electrocatalytic activity. FIG. 9 (a) shows Ni 2 P/Co 2 P continuously tests the current change condition of 48h under overpotential of-166 mV, -186mV and-216 mV respectively, and the current density is almost not attenuated under lower overpotential, and fluctuates under higher overpotential, but still maintains higher value, and Ni is seen 2 P/Co 2 P has good HER stability. FIG. 9 (b) is a comparison of polarization curves before and after a long-term test of the material at 50h (-166 mV overpotential), with the two curves almost completely overlapping, illustrating the Ni produced 2 P/Co 2 P is excellentAnd (4) durability.
Example 3:
preparation, characterization and performance test of nickel disulfide/cobalt disulfide submicron flower cluster
The Ni (OH) obtained in example 1 was added 2 /Co(OH) 2 The material and sublimed sulfur were placed downstream and upstream of the porcelain boat, respectively, at a mass ratio of 1 -1 Heating to 350 deg.C, maintaining for 120min, and naturally cooling to room temperature to obtain the final product 2 /CoS 2 . FIG. 10 is an XRD spectrum of the prepared material. Each obvious characteristic peak is in NiS 2 Standard card (PDF # 11-0099) and CoS 2 Middle position of peak position of standard card (PDF # 41-1471): the peak at 32.22 ° belongs to NiS 2 (200) At 31.59 ℃ and CoS 2 (200) Superposition results at 32.30 °; the peak at 35.82 ℃ is NiS 2 (210) At 35.31 ℃ and CoS 2 (210) Combined results at 36.24 °; the peak at 54.16 ℃ is NiS 2 (230) At 53.65 ℃ and CoS 2 (230) Superimposed result at 54.94 °; the occurrence of such superposition and offset proves NiS 2 /CoS 2 The formation of bimetallic sulfides. FIG. 11 (a) shows NiS 2 /CoS 2 The FESEM image of (1), FIG. 11 (b) is a further enlarged FESEM image, which demonstrates that NiS is present 2 /CoS 2 Is a uniform submicron floral structure.
FIG. 12 is the NiS prepared 2 /CoS 2 And commercial Pt/C in N 2 1mol L of saturation -1 Polarization curve of electrochemical test carried out in KOH solution, scan rate 2mV s -1 And corrected by iR compensation. From the figure, niS 2 /CoS 2 At 10mA cm -2 HER overpotential at current density was 0.336V, 306mV higher than commercial Pt/C.
Example 4:
preparation, characterization and performance test of nickel diselenide/cobalt diselenide submicron flower cluster
The Ni (OH) obtained in example 1 was added 2 /Co(OH) 2 The material and selenium powder are respectively arranged at the downstream and the upstream of the porcelain boat according to the mass ratio of 1. Under argon atmosphere at 2 deg.C for min -1 The temperature rise rate is raised to 350 DEG CKeeping the temperature for 2h, and naturally cooling to room temperature to obtain the bimetallic sulfide NiSe 2 /CoSe 2 . FIG. 13 is an XRD spectrum of the prepared material, each distinct characteristic peak of which is at NiSe 2 (PDF # 41-1495) and CoSe 2 (PDF # 09-0234) middle position of peak. Specifically, the diffraction peak at 33.88 ℃ is NiSe 2 At 33.41 ℃ and CoSe 2 Results at 34.20 ℃ both ascribed (210) crystal plane; niSe having a peak at 37.22 ℃ of 36.70 DEG 2 And CoSe at 37.62 ° 2 All of the diffraction peaks of (a) correspond to the respective (211) crystal planes; the diffraction peak at 51.22 ℃ is NiSe 2 At 50.48 ℃ and CoSe 2 Results at 51.75 ° all ascribed to the (311) crystal plane; the peak at 58.34 ℃ is NiSe 2 At 57.53 ℃ and CoSe 2 Results at 58.85 ° each correspond to a respective (321) crystal plane; the occurrence of this shift also proves that the bimetallic selenide NiSe 2 /CoSe 2 Is performed. FIGS. 14 (a) and (b) are NiSe 2 /CoSe 2 From the low power and high power FESEM images, niSe can be found 2 /CoSe 2 Also a uniform sub-micron floral cluster structure.
FIG. 15 shows NiSe being produced 2 /CoSe 2 And commercial Pt/C in N 2 1mol L of saturation -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 And through iR compensation correction, niSe can be seen from the figure 2 /CoSe 2 At 10mA cm -2 HER overpotential at current density was 0.366V, 336mV higher than commercial Pt/C.
Example 5:
preparation and test of nickel oxide/cobalt oxide submicron flower cluster
The Ni (OH) obtained in example 1 was added 2 /Co(OH) 2 Spreading the material in a porcelain boat at 2 deg.C for min -1 The temperature rising rate is raised to 350 ℃ in the air, the temperature is kept for 2h, and the temperature is naturally cooled to the room temperature, so that the bimetallic oxide NiO/CoO is obtained. FIG. 16 is an XRD spectrum of the prepared material, and it can be seen that the diffraction peaks are located entirely between the NiO standard card (PDF # 47-1049) and the CoO standard card (PDF # 48-1719). The peak of NiO/CoO is shifted to the right and left with respect to the pure NiO and CoO phases, respectively, and the peak at 37.25 ℃ is the combined result of NiO at 37.68 ℃ and CoO at 36.5 ℃, both pairsThe respective (111) crystal plane. The peak at 42.50 ° is the superposition of NiO at 43.28 ° (200) and CoO at 42.39 ° (200); the peak at 62.46 ℃ is the result of NiO at 62.88 ℃ and CoO at 61.50 ℃ and corresponds to the respective (220) crystal planes. This crystallographic plane is uniform and the shift of the diffraction peak evidences the formation of the bimetallic oxide NiO/CoO.
FIG. 17 (a) is a low power FESEM image of NiO/CoO and FIG. 17 (b) is a high power FESEM image, and it can be found that the diameter of the NiO/CoO submicron flower clusters is about 550nm.
FIG. 18 shows the NiO/CoO and commercial Pt/C in N prepared 2 Saturated 1mol L -1 Polarization curve of electrochemical test carried out in KOH solution, scan rate 2mV s -1 And through iR compensation correction, niO/CoO is shown to be at 10mA cm -2 The HER overpotential at current density was 0.313V, 283mV higher than commercial Pt/C.
Example 6:
preparation of nickel hydroxide/cobalt hydroxide submicron flower cluster with hydrolysis time of 5h
The difference from example 1 is that step (2) "transfer the dispersion to a 50mL hydrothermal reaction kettle and place the kettle in an oven at 160 ℃ for 7h to allow the nickel cobalt glycerate submicron spheres to hydrolyze to hydroxide" instead "transfer the dispersion to a 50mL hydrothermal reaction kettle and place the kettle in an oven at 160 ℃ for 5h to allow the nickel cobalt glycerate submicron spheres to hydrolyze to hydroxide".
FIG. 19 shows prepared Ni (OH) 2 /Co(OH) 2 XRD spectrum of (1). As can be seen from fig. 1, the diffraction peak =2 θ in the XRD spectrogram shows a cliff-like rise around 34 °, which proves that the materials have ultra-thin structural characteristics, and the sharp diffraction peaks at 25 ° and 60 ° prove that the materials have good crystallinity. As can be seen from the FESEM image shown in FIG. 20, ni (OH) 2 /Co(OH) 2 Microscopically, the three-dimensional flower cluster structure is formed by orderly stacking two-dimensional nano sheets, which indicates that the submicron flower cluster of the nickel cobalt hydroxide can still be obtained after the hydrolysis time is shortened to 5 hours.
Example 7:
preparation of nickel hydroxide/cobalt hydroxide submicron flower cluster with hydrolysis time of 9h
The difference from example 1 is that step (2) "transfer the dispersion to a 50mL hydrothermal reaction kettle and place the kettle in an oven at 160 ℃ for 7h to allow the nickel cobalt glycerate submicron spheres to hydrolyze to hydroxide" instead "transfer the dispersion to a 50mL hydrothermal reaction kettle and place the kettle in an oven at 160 ℃ for 9h to allow the nickel cobalt glycerate submicron spheres to hydrolyze to hydroxide".
FIG. 21 shows prepared Ni (OH) 2 /Co(OH) 2 XRD spectrum of (1). As can be seen from fig. 22, the diffraction peak =2 θ in the XRD spectrogram shows a cliff-like rise around 34 °, which proves that the materials have ultra-thin structural characteristics, and the sharp diffraction peaks at 25 ° and 60 ° prove that the materials have good crystallinity. As can be seen from the FESEM image shown in FIG. 22, ni (OH) 2 /Co(OH) 2 Microscopically, the structure of the three-dimensional flower cluster is formed by orderly stacking two-dimensional nano sheets, which shows that the submicron flower cluster of the nickel-cobalt hydroxide can still be obtained after the hydrolysis time is prolonged to 9 hours.
Example 8:
preparation and test of nickelous phosphide/cobaltous phosphide submicron flower cluster with hydrolysis time of 5h
Ni (OH) obtained in example 6 2 /Co(OH) 2 The material and the sodium hypophosphite are respectively arranged at the downstream and the upstream of the porcelain boat according to the mass ratio of 1. Under argon atmosphere at 2 deg.C for min -1 The temperature rising rate is increased to 350 ℃, the temperature is kept for 2 hours at 350 ℃, and the mixture is naturally cooled to the room temperature to obtain the bimetallic phosphide Ni 2 P/Co 2 And P material. FIG. 23 is an XRD spectrum of the prepared material, with diffraction peaks 2 θ =44.6 °, 47.3 °, 54.2 ° and 74.7 ° with Ni 2 The (201), (210), (300) and (400) crystal planes of the P standard card (PDF # 03-0953) correspond to the diffraction peaks 2 theta =40.7 °, 41.0 ° and 43.3 ° of Co 2 The (121), (201) and (211) crystal faces of the P standard card (PDF # 32-0306) correspond to each other, so the prepared material is Ni 2 P phase and Co 2 And (4) P phase. Ni from FIG. 24 2 P/Co 2 The FESEM image of the P sample shows that the two-dimensional nanosheet of the material is thicker and rich in wrinkles, and Ni can be obtained 2 P/Co 2 P sample isUniform submicron bouquet structure.
FIG. 25 shows prepared Ni 2 P/Co 2 P and commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve in KOH electrolyte with scan rate of 2mV s -1 And corrected by iR compensation, ni is shown in the figure 2 P/Co 2 P is at 10mA cm -2 The overpotential at current density was 0.229V, 199mV higher than commercial Pt/C.
Example 9:
preparation and test of nickelous phosphide/cobaltous phosphide submicron flower cluster with hydrolysis time of 9h
Ni (OH) obtained in example 7 2 /Co(OH) 2 The material and sodium hypophosphite are respectively arranged at the downstream and the upstream of the porcelain boat according to the mass ratio of 1. Under argon atmosphere at 2 deg.C for min -1 Heating to 350 ℃, keeping the temperature at 350 ℃ for 2 hours, and naturally cooling to room temperature to obtain the bimetallic phosphide Ni 2 P/Co 2 And P material. FIG. 26 is an XRD spectrum of the prepared material, with diffraction peaks 2 θ =44.6 °, 47.3 °, 54.2 ° and 74.7 ° with Ni 2 The (201), (210), (300) and (400) crystal planes of the P standard card (PDF # 03-0953) correspond to the diffraction peaks 2 theta =40.7 °, 41.0 ° and 43.3 ° of Co 2 The (121), (201) and (211) crystal faces of the P standard card (PDF # 32-0306) correspond to each other, so the prepared material is Ni 2 P phase and Co 2 And (4) P phase. Ni obtained from FIG. 27 2 P/Co 2 The FESEM image of the P sample can show that the two-dimensional nanosheet of the material is thick and has wrinkles, and the two-dimensional nanosheet of the material is thick and has wrinkles, so that Ni can be obtained 2 P/Co 2 The P sample is a uniform sub-micron cluster structure.
FIG. 28 shows prepared Ni 2 P/Co 2 P and commercial Pt/C in N 2 Saturated 1mol L -1 Polarization curve in KOH electrolyte, scan rate 2mV s -1 And corrected by iR compensation, ni is shown in the figure 2 P/Co 2 P is at 10mA cm -2 The overpotential at current density was 0.204V, 174mV higher than commercial Pt/C.
Example 10:
preparation of nickel hydroxide/cobalt hydroxide submicron flower cluster with low nickel and cobalt contents
The Ni (NO) of step (1) of example 1 was reacted 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·9H 2 The mass of O was changed to 20mg, and other preparation parameters were the same as in example 1. The diameter of the obtained glycerate spheres is reduced to some extent, the thickness of the obtained nano petal pieces after hydrolysis is obviously reduced, the minimum is 2nm, and the diameter of the submicron flower cluster is about 500nm.
Example 11:
preparation of nickel hydroxide/cobalt hydroxide submicron flower cluster with high nickel and cobalt contents
Ni (NO) obtained in step (1) of example 1 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·9H 2 The mass of O was changed to 80mg, and other preparation parameters were the same as in example 1. The diameter of the obtained glycerate ball is larger, the thickness of the nanometer petal sheet obtained after hydrolysis is obviously thickened and can reach 30nm, and the diameter of the submicron flower cluster is 600-650 nm.
Example 12:
preparation of nickelous phosphide/cobaltous phosphide submicron flower clusters with thick petal pieces
The Ni (OH) obtained as described in example 2 was reacted 2 /Co(OH) 2 The material and sodium hypophosphite are mixed in an argon atmosphere at 2 ℃ for min -1 The temperature rise rate of (2) is increased to 350 ℃ and the temperature is kept for 2h, and is changed to 500 ℃ and the temperature is kept for 2h, and other parameters are the same as those of the embodiment 2. The obtained petals of the nickelous phosphide/cobaltous phosphide submicron flower cluster are obviously thickened, and crystal grains are gathered and grown.
Example 13:
preparation of submicron nickel disulfide/cobalt disulfide flower clusters with thicker petal pieces
The Ni (OH) obtained in example 3 was reacted 2 /Co(OH) 2 Mixing the material with sublimed sulfur at 2 deg.C for min under argon atmosphere -1 The temperature rising rate of (2) is increased to 350 ℃ and kept for 120min, and is changed to be increased to 500 ℃ and kept for 120min, and other parameters are the same as those of the embodiment 3. The petal pieces of the obtained nickel disulfide/cobalt disulfide submicron flower clusters are obviously thickened, and crystal grains are gathered and grown.
Example 14:
preparation of submicron nickel diselenide/cobalt diselenide flower clusters with thicker petal pieces
Mixing Ni (OH) described in example 4 2 /Co(OH) 2 Mixing the material with selenium powder at 2 deg.C for min under argon atmosphere -1 The temperature rising rate of (2) was increased to 350 ℃ and kept at the temperature for 2 hours, and instead, the temperature was increased to 500 ℃ and kept at the temperature for 2 hours, with the other parameters being the same as those in example 4. The obtained petals of the nickel diselenide/cobalt diselenide submicron flower clusters are obviously thickened, and crystal grains are gathered and grown.
Example 15:
preparation and test of nickel oxide/cobalt oxide submicron flower clusters with thick petal pieces
Mixing Ni (OH) described in example 5 2 /Co(OH) 2 The material was raised to 350 ℃ in air and held for 2h, instead raised to 500 ℃ and held for 2h, with the other parameters being the same as in example 5. The petal pieces of the obtained nickel oxide/cobalt oxide submicron flower clusters are obviously thickened, and crystal grains are gathered and grown.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The nickel-cobalt bimetal-based submicron flower cluster is characterized in that the nickel hydroxide/cobalt hydroxide submicron flower cluster with the diameter of 500-650 nm is formed by preparing a plurality of nanometer flower petals with the thickness of 2-30 nm by using nickel hydroxide/cobalt hydroxide as components, wherein the content of nickel and cobalt is 1: (1-4) or (1-4): 1; and the nickel hydroxide/cobalt hydroxide submicron flower cluster is used as a substrate to prepare a nickelous phosphide/cobaltous phosphide submicron flower cluster or a nickel disulfide/cobalt disulfide submicron flower cluster or a nickel diselenide/cobalt diselenide submicron flower cluster or a nickel oxide/cobalt oxide submicron flower cluster.
2. The method for preparing the nickel-cobalt bi-metal based submicron flower cluster according to claim 1, characterized by comprising the following steps:
(1) Preparation of nickel cobalt glycerate submicron sphere precursor
Nickel salt according to mass/volume ratio: isopropyl alcohol = (0.5 to 2): 1mg/mL and cobalt salt: isopropyl alcohol = (0.5 to 2): 1mg/mL, dissolving nickel salt and cobalt salt in isopropanol to obtain a nickel-cobalt salt solution; glycerol in volume ratio: the nickel cobalt salt solution is 1: (3-7) adding glycerol, performing ultrasonic treatment for 10-20 min, transferring the mixture into a hydrothermal reaction kettle, and keeping the temperature at 150-200 ℃ for 15-20 h; washing with absolute ethyl alcohol, drying at 40-80 ℃ for 5-10 h to obtain nickel cobalt glycerate submicron spheres;
(2) Preparation of nickel hydroxide/cobalt hydroxide submicron flower cluster
The method comprises the following steps of (1) preparing nickel cobalt glycerate submicron spheres according to the mass/volume ratio: deionized water = (0.5 to 5): 1mg/mL, dispersing the nickel cobalt glycerate submicron spheres obtained in the step (1) in deionized water, carrying out ultrasonic treatment for 15-30 min, transferring the dispersion liquid into a hydrothermal reaction kettle, and carrying out heat preservation at 150-200 ℃ for 5-9 h to hydrolyze the nickel cobalt glycerate submicron spheres and convert the nickel cobalt glycerate submicron spheres into nickel hydroxide/cobalt hydroxide submicron clusters;
(3) Preparation of nickelous phosphide/cobaltous phosphide or nickel disulfide/cobaltous disulfide or nickel diselenide/cobaltous diselenide or nickel oxide/cobalt oxide submicron flower cluster
(3-1) mixing the nickel hydroxide/cobalt hydroxide submicron flower clusters obtained in the step (2) and a phosphorus source according to a mass ratio of 1: (10-15) respectively placing the ceramic boats at the downstream and the upstream, placing the ceramic boats in a tubular furnace, calcining the ceramic boats to 300-500 ℃ in an inert atmosphere, preserving the heat for 90-180 min, and cooling to obtain the nickelous phosphide/cobaltous phosphide submicron flower clusters;
(3-2) mixing the nickel hydroxide/cobalt hydroxide submicron flower cluster obtained in the step (2) and sublimed sulfur according to the mass ratio of 1: (2-5) respectively placing the ceramic boat at the downstream and the upstream, placing the ceramic boat in a tube furnace, calcining the ceramic boat to 300-500 ℃ in an inert atmosphere, preserving the heat for 90-180 min, and cooling to obtain the nickel disulfide/cobalt disulfide submicron floriation;
(3-3) mixing the nickel hydroxide/cobalt hydroxide submicron flower clusters obtained in the step (2) and selenium powder according to the mass ratio of 1: (3-7) respectively placing the ceramic boat at the downstream and the upstream, placing the ceramic boat in a tube furnace, calcining the ceramic boat to 300-500 ℃ in an inert atmosphere, preserving the heat for 90-180 min, and cooling to obtain the nickel diselenide/cobalt diselenide submicron flower clusters;
and (3-4) calcining the nickel hydroxide/cobalt hydroxide submicron flower cluster obtained in the step (2) in air to 300-500 ℃, preserving the temperature for 90-180 min, and cooling to obtain the nickel oxide/cobalt oxide submicron flower cluster.
3. The method for preparing the nickel-cobalt bimetal based submicron flower cluster according to the claim 2, characterized in that the nickel salt in the step (1) is nickel nitrate or nickel acetate or nickel chloride.
4. The method for preparing the nickel-cobalt bimetallic-based submicron flower cluster as claimed in claim 2, wherein the cobalt salt in the step (1) is cobalt nitrate or cobalt acetate or cobalt chloride.
5. The method of claim 2, wherein the phosphorus source in step (3) is sodium hypophosphite or red phosphorus.
6. The method for preparing nickel-cobalt bimetallic-based submicron flower clusters according to claim 2, characterized in that the heating rate of calcining to 300-500 ℃ in inert atmosphere in step (3) is 1-5 ℃/min.
7. The method for preparing the nickel-cobalt bi-metal based submicron flower cluster according to claim 2, characterized in that the inert atmosphere in the step (3) is nitrogen or argon.
8. The method for preparing the nickel-cobalt bimetal based submicron flower cluster according to claim 2, characterized in that the temperature rise rate of calcining in air to 300-500 ℃ in the step (3) is 1-5 ℃/min.
9. Use of a nickel-cobalt bimetallic-based sub-micron cluster of flowers according to claim 1, as hydrogen evolution electrocatalyst.
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