CN113955728A - Preparation of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide and its application in water electrolysis - Google Patents
Preparation of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide and its application in water electrolysis Download PDFInfo
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- CN113955728A CN113955728A CN202111080749.8A CN202111080749A CN113955728A CN 113955728 A CN113955728 A CN 113955728A CN 202111080749 A CN202111080749 A CN 202111080749A CN 113955728 A CN113955728 A CN 113955728A
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- cobalt
- phosphide
- manganese
- electrode material
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 86
- 239000010941 cobalt Substances 0.000 title claims abstract description 86
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 86
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 title claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000007772 electrode material Substances 0.000 claims abstract description 68
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 32
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 32
- 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 abstract description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 60
- 238000012360 testing method Methods 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000010411 electrocatalyst Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 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 5
- 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 5
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 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 5
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 5
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 5
- 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 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052786 argon Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 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 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition metal sulfides Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 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 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C01B25/088—Other phosphides containing plural metal
-
- 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
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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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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- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- 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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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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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- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Abstract
The invention discloses a preparation method of hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide, which utilizes processed foam nickel and comprises the following steps: mixing cobalt nitrate, ammonium fluoride, urea and deionized water; adding the mixed solution and the treated nickel foam into a reaction kettle, and then carrying out hydrothermal reaction to obtain a cobalt hydroxide precursor material; adding a potassium permanganate solution and a cobalt hydroxide precursor material into the reaction kettle, and then carrying out hydrothermal reaction again to obtain a cobalt hydroxide/manganese oxide electrode material; and carrying out a phosphating reaction on the cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder to obtain the cobalt phosphide/cobalt manganese phosphide electrode material. The cobalt phosphide/cobalt manganese phosphide electrode material can be used for HER/OER dual-function catalytic water electrolysis.
Description
Technical Field
The invention belongs to the technical field of electrolytic water electrode material preparation, and particularly relates to a preparation method of a hollow-grade-structure cobalt phosphide/cobalt manganese phosphide material and application of the material in bifunctional catalytic electrolytic water.
Background
With the rapid increase in global energy demand and the growing environmental problems, people are continuously forced to seek new generation of renewable, high-efficiency and clean energy to replace the traditional fossil fuels. Hydrogen is an ideal clean energy source, has the advantages of high energy density and zero carbon dioxide emission, and the hydrogen production by water electrolysis is undoubtedly an efficient, convenient and sustainable hydrogen production technology. The electrolytic water reaction consists of two half reactions, namely a cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction. However, in practical applications, a large overpotential is required to achieve the desired water splitting current density, and therefore, it is necessary to find an efficient electrocatalyst. At present, Pt/C and RuO2、IrO2The noble metal-based catalyst has high activity on HER and OER, and is the best catalyst material in the field of hydrogen production by water electrolysis at present. However, these precious metals are present in small amounts in the earth and are expensive, making their large-scale commercial use impractical. Therefore, it is very important to develop an electrocatalyst with a lower overpotential to realize low-cost, efficient and stable hydrogen production by water electrolysis.
Transition metal (e.g., Fe, Co, Ni, and Mn) based electrocatalysts have attracted considerable attention and are widely recognized as ideal substitutes for HER and OER noble metal based materials due to their low cost and excellent electrocatalytic properties. Such as transition metal oxides, transition layered double hydroxides, metal organic framework materials, transition metal phosphides, transition metal sulfides, etc. Conventional transition metal-based electrocatalysts are generally formed from aggregated particles, whereas bulk metal-based electrocatalysts do not have a competitive advantage due to their limited active surface area and few catalytically active sites. Meanwhile, most of the catalysts have poor electrocatalytic performance on electrolyzed water due to the limitation of microscopic morphology and single material. In order to overcome the above disadvantages, various schemes have been devised in the aspects of interface engineering, composition design and morphology optimization to achieve enhancement of electrocatalytic performance. The structure of the material has great influence on the electrocatalysis performance, the three-dimensional structure electrocatalyst is reasonably designed, the specific surface area can be effectively increased, the catalytic activity sites can be further improved, and the electrocatalysis performance can be effectively improved by accurately controlling the form and the structure of the electrocatalyst.
Publication No. CN105107536A discloses a preparation method of a polyhedral cobalt phosphide catalyst for water electrolysis hydrogen production, which comprises the steps of firstly obtaining a polyhedral metal organic framework ZIF-67 through cobalt nitrate, 2-methylimidazole and methanol; and then calcining the ZIF-67 in the air atmosphere to obtain cobaltosic oxide, and phosphorizing the cobaltosic oxide in the inert atmosphere to obtain the polyhedral cobaltous phosphide catalyst for hydrogen production by electrolyzing water, wherein although the prepared cobaltous phosphide catalyst material has high crystallinity, the polyhedral morphology of a metal organic framework template is maintained, the preparation process flow is simple, a binder is required during electrode manufacturing, and meanwhile, the oxygen evolution performance is not researched.
The publication No. CN112246261A discloses a cobalt phosphide hierarchical porous nanowire material, its preparation and application in the hydrogen production reaction by electrolyzing water, firstly synthesizing basic cobalt carbonate nanowire, then carrying out controllable phosphorization under inert atmosphere, phosphorization and air hole formation are carried out simultaneously, although in the synthesized cobalt phosphide hierarchical porous nanowire material, a large number of air holes are distributed in the cobalt phosphide nanowire to form a hierarchical porous structure, a binder is needed when manufacturing an electrode, the stability of the electrode material is affected, and simultaneously the hydrogen evolution activity is not good.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a cobalt phosphide/cobalt manganese phosphide material with a hollow hierarchical structure.
In order to solve the technical problem, the invention provides a preparation method of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide, which utilizes the processed foam nickel and comprises the following steps:
s1, adding cobalt nitrate, ammonium fluoride and urea into deionized water, and stirring at room temperature until the cobalt nitrate, the ammonium fluoride and the urea are dissolved to obtain a mixed solution;
cobalt nitrate: ammonium fluoride: the molar ratio of urea to urea is 1 (2 plus or minus 0.2) to (4 plus or minus 0.4);
in the mixed solution, the concentration of the cobalt nitrate is 4 +/-0.5 mmol/100 mL;
s2, adding the mixed solution (about 25mL) obtained in the step S1 and the treated nickel foam (1 piece) into a reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), and carrying out hydrothermal reaction at 120 +/-20 ℃ for 6 +/-1 h;
after the reaction is finished and the temperature is cooled to room temperature, taking out the reacted foam nickel, cleaning and drying in vacuum to obtain a cobalt hydroxide precursor material;
s3, adding a potassium permanganate solution (about 30mL) and the cobalt hydroxide precursor material obtained in the step S2 into a reaction kettle (a stainless steel reaction kettle with a polytetrafluoroethylene lining), and carrying out hydrothermal reaction at 90-150 ℃ for 1 +/-0.1 h;
after the reaction is finished and the temperature is cooled to room temperature, taking out the cobalt hydroxide precursor material after the reaction, cleaning and vacuum drying to obtain a cobalt hydroxide/manganese oxide electrode material;
and S4, carrying out a phosphating reaction on the cobalt hydroxide/manganese oxide electrode material obtained in the step S3 and sodium hypophosphite powder to obtain a cobalt phosphide/cobalt manganese phosphide electrode material (namely, cobalt phosphide/cobalt manganese phosphide with a hollow hierarchical structure).
The improvement of the preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is as follows: the S4 is as follows:
respectively putting the cobalt hydroxide/manganese oxide electrode material and sodium hypophosphite powder into two porcelain boats, then putting the two porcelain boats into a tubular furnace with an inert gas inlet pipe, heating to 350 +/-50 ℃ under the protection of inert gas (such as argon), and preserving heat for 2 +/-0.5 h, thereby phosphorizing the cobalt hydroxide/manganese oxide electrode material into cobalt phosphide/cobalt manganese phosphide.
Description of the drawings: after the reaction is finished, cooling to room temperature under the protection of inert gas (such as argon) to obtain the cobalt phosphide/cobalt manganese phosphide electrode material.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
in the step S4, the heating rate is 2 +/-0.5 ℃/min.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
in the S4, in the tube furnace, the porcelain boat filled with sodium hypophosphite is close to the gas inlet of the inert gas, and the porcelain boat filled with the cobalt hydroxide/manganese oxide electrode material is close to the gas outlet of the inert gas;
the cobalt hydroxide/manganese oxide electrode material prepared by each piece of 2cm multiplied by 3cm of foamed nickel is matched with 300 plus or minus 50mg of sodium hypophosphite.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
the vacuum drying temperature in the S2 is 70 +/-10 ℃, and the drying time is 12 +/-1 h;
the temperature of vacuum drying in the S3 is 70 +/-10 ℃, and the drying time is 12 +/-1 h.
The cleaning in the step S2 is as follows: ultrasonic cleaning with deionized water and absolute ethyl alcohol respectively;
the cleaning in the step S3 is as follows: and respectively ultrasonically cleaning by using deionized water and absolute ethyl alcohol.
The preparation method of the hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide is further improved as follows:
in the S3, the concentration of the potassium permanganate solution is 0.02-0.04M (preferably 0.03M).
The invention also provides the application of the hollow-grade-structure cobalt phosphide/cobalt manganese phosphide prepared by the method: used for HER/OER dual-function catalytic water electrolysis.
In the present invention: the treatment method of the foamed nickel comprises the following steps:
a. adding hydrochloric acid solution with the concentration of 3 +/-1 mol/L into a beaker, then adding a plurality of pieces of foam nickel which is cut into 2cm multiplied by 3cm into the beaker containing the hydrochloric acid, sealing the opening of the beaker by using a preservative film, and ultrasonically cleaning for 30 +/-10 min;
b. taking the foamed nickel subjected to ultrasonic treatment out of the beaker, and washing the foamed nickel by using deionized water until the pH value of the washing water is neutral; then ultrasonic cleaning is carried out by using deionized water and absolute ethyl alcohol respectively to ensure that the surface of the foamed nickel is clean;
c. and after the foamed nickel is washed clean, placing the foamed nickel in a vacuum oven to be dried at 70 +/-10 ℃ (the time is about 12 +/-2 h) to obtain the treated foamed nickel.
The invention has the advantages of simple preparation process, low cost and excellent electrocatalytic performance. Firstly, carrying out acid pickling treatment on foamed nickel, firstly, carrying out hydrothermal reaction on the foamed nickel to grow cobalt hydroxide, and then, growing manganese oxide on a cobalt hydroxide precursor through secondary hydrothermal, namely, growing cobalt hydroxide/manganese oxide on the foamed nickel through a two-step hydrothermal method, then, using sodium hypophosphite as a phosphorus source, and phosphorizing the cobalt hydroxide/manganese oxide on the surface of the foamed nickel at low temperature to obtain cobalt phosphide/cobalt manganese phosphide, thereby preparing the cobalt phosphide/cobalt manganese phosphide dual-function electrode material which has no binder, large specific surface area, hollow hierarchical structure and excellent electro-catalytic performance.
The invention has the following technical advantages:
1. the invention has simple process, low cost and excellent electrocatalysis performance;
2. the cobalt phosphide/cobalt manganese phosphide electrode material is prepared by taking foamed nickel as a substrate, and no binder is used, so that good mechanical adhesion and good conductivity and stability are ensured;
3. the hollow-grade porous structure provides a larger specific surface area, and can expose more catalytic active sites, thereby improving the electron transfer efficiency and providing a smooth channel for the effective release of gas;
4. the synergistic effect of the cobalt-manganese double metals enriches catalytic active sites while enhancing the conductivity, and the phosphating treatment can adjust an electronic structure and form defects, thereby improving the catalytic activity.
In conclusion, the invention takes the foamed nickel as the substrate, improves the conductivity of the electrode by the synergy of cobalt and manganese double metals, the specific surface area of the hollow hierarchical structure is increased, and the phosphorization effect, and the prepared hollow hierarchical structure cobalt phosphide/cobalt manganese phosphide material with excellent performance has excellent HER and OER electrocatalytic activity and good stability. The electrode material prepared by the invention has excellent conductivity, large specific surface area and abundant catalytic active sites; the prepared cobalt phosphide/cobalt manganese phosphide material has excellent catalytic activity as a bifunctional electrocatalyst for Hydrogen Evolution (HER) and Oxygen Evolution (OER), and has good application prospect in the field of full water splitting.
Namely, the hollow grade material obtained by the invention has larger specific surface area, more catalytic active sites and rapid transmission channels, and good catalytic performance; as a bifunctional electrocatalyst, hydrogen evolution and oxygen evolution properties were studied simultaneously.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is an XRD diffraction pattern of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 2 is a scanning electron micrograph of a cobalt phosphide/cobalt manganese phosphide electrode material uniformly grown on foamed nickel produced in example 1.
FIG. 3 is a transmission electron micrograph of a cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 4 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
Figure 5 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 1.
FIG. 6 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 2.
Figure 7 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 2.
FIG. 8 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 3.
Figure 9 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in example 3.
FIG. 10 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-1.
FIG. 11 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-1.
FIG. 12 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-2.
FIG. 13 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 1-2.
FIG. 14 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-1.
FIG. 15 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-1.
FIG. 16 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-2.
FIG. 17 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 2-2.
FIG. 18 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-1.
FIG. 19 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-1.
FIG. 20 is an OER linear voltammogram (LSV) scan of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-2.
FIG. 21 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 3-2.
FIG. 22 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-1.
FIG. 23 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-1.
FIG. 24 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-2.
FIG. 25 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 4-2.
FIG. 26 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-1.
FIG. 27 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-1.
FIG. 28 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-2.
FIG. 29 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 5-2.
FIG. 30 is an OER linear voltammogram (LSV) scan of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-1.
FIG. 31 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-1.
FIG. 32 is an OER linear voltammetric sweep (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-2.
FIG. 33 is a HER linear voltammetric scan (LSV) of the cobalt phosphide/cobalt manganese phosphide electrode material prepared in comparative example 6-2.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
in the present invention, ultrasonic cleaning is generally performed at room temperature for 10 min.
The preparation method of the processed foam nickel comprises the following steps:
a. adding hydrochloric acid solution with the concentration of 3mol/L into a beaker, then adding a plurality of pieces of foam nickel which is cut into 2cm multiplied by 3cm into the beaker containing the hydrochloric acid, sealing the opening of the beaker by using a preservative film, and ultrasonically cleaning for 30 min;
b. taking the foamed nickel subjected to ultrasonic treatment out of the beaker, and washing the foamed nickel by using deionized water until the pH value of the washing water is neutral; then ultrasonic cleaning is carried out by using deionized water and absolute ethyl alcohol respectively to ensure that the surface of the foamed nickel is clean;
c. and after the foamed nickel is washed clean, placing the foamed nickel in a vacuum oven for drying treatment at 70 ℃, and drying for 12h to obtain the treated foamed nickel.
The following examples all used stainless steel reactors lined with polytetrafluoroethylene.
Example 1, a method for preparing a cobalt phosphide/cobalt manganese phosphide electrode material, sequentially comprising the following steps:
1) sequentially adding 1mmol of cobalt nitrate, 2mmol of ammonium fluoride and 4mmol of urea into a beaker filled with 25mL of deionized water, and stirring at room temperature until the cobalt nitrate, the ammonium fluoride and the urea are dissolved;
2) transferring all the mixed solution obtained in the step 1) into a reaction kettle, simultaneously putting the treated piece of foamed nickel into the reaction kettle, transferring the reaction kettle into a high-temperature oven, and reacting for 6 hours at 120 ℃; after the reaction is finished, after the oven is cooled to room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol;
putting the washed foam nickel into a vacuum oven to be dried for 12 hours at 70 ℃ to obtain a cobalt hydroxide precursor material;
3) firstly, adding 30mL of 0.03M potassium permanganate solution into a reaction kettle, then putting the cobalt hydroxide precursor material obtained in the step 2) into the reaction kettle, transferring the reaction kettle into a high-temperature oven, and reacting for 1h at 120 ℃; after the reaction is finished, after the oven is cooled to room temperature, taking out the foamed nickel, and respectively carrying out ultrasonic cleaning by using deionized water and absolute ethyl alcohol; then placing the mixture in a vacuum oven to dry for 12 hours at 70 ℃ to obtain a cobalt hydroxide/manganese oxide electrode material;
4) respectively placing the cobalt hydroxide/manganese oxide electrode material (one piece) obtained in the step 3) and 300mg of sodium hypophosphite powder into two porcelain boats, then placing the two porcelain boats in the center of a tube furnace, wherein the tube furnace is provided with an argon gas inlet pipe, placing the porcelain boat filled with the sodium hypophosphite at one side close to the argon gas inlet of the tube furnace, and placing the porcelain boat filled with the cobalt hydroxide/manganese oxide electrode material at one side of a gas outlet;
opening a heating switch of the tubular furnace under the argon atmosphere, heating the tubular furnace from room temperature to 350 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours at the temperature, so as to phosphorize the cobalt hydroxide/manganese oxide electrode material into cobalt phosphide/cobalt manganese phosphide;
and after the phosphating reaction is finished (namely the set heat preservation time is up), continuously cooling the temperature in the tubular furnace to room temperature under the argon atmosphere to obtain the cobalt phosphide/cobalt manganese phosphide electrode material.
And carrying out electrochemical performance test on the prepared cobalt phosphide/cobalt manganese phosphide electrode material.
FIG. 1 is an XRD diffraction pattern of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in the embodiment 1, and from XRD test curves, it can be seen that diffraction peaks at 44.3 °, 51.6 ° and 76.1 ° respectively correspond to (111), (200) and (220) crystal planes of nickel, and are consistent with the XRD standard card PDF #04-0850 of nickel; diffraction peaks at 31.7 degrees, 36.4 degrees and 48.3 degrees respectively correspond to (011), (111) and (211) crystal faces of cobalt phosphide and are matched with an XRD standard card PDF #29-0497 of the cobalt phosphide; the diffraction peak of cobalt manganese phosphide is not very significant because the crystallinity of the sample is poor and the content of manganese is low. Fig. 2 is a scanning electron microscope topography of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in the present example 1, wherein the cobalt phosphide/cobalt manganese phosphide shown in fig. 2 is in a grade structure, and the nano-arrays are uniformly grown on the foamed nickel substrate. Fig. 3 is a transmission electron microscope topography of the hollow grade cobalt phosphide/cobalt manganese phosphide electrode material prepared in the embodiment 1, and it can be seen from fig. 3 that the cobalt phosphide/cobalt manganese phosphide is of a hollow structure, the hollow structure is formed by stacking nanosheets, and some porous structures can be seen at the same time.
Experiment, OER, HER test:
preparation of test samples: the cobalt phosphide/cobalt manganese phosphide electrode material was cut into a "convex" shape comprising a square area of 1cm × 1cm (i.e., the lower half of the "convex" shape was 1cm × 1cm, and the upper half was 0.5cm × 0.5cm) as a test sample.
A test sample is taken as a working electrode, a platinum sheet is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, a test instrument is a CHI 760E type electrochemical workstation in Shanghai Chen Hua, a 1M KOH solution is used as an electrolyte, and a linear volt-ampere scanning test (the scanning speed is 1mV/s) is carried out at room temperature to detect the electrocatalysis performance of the cobalt phosphide/cobalt manganese phosphide electrode. The potentials described hereinafter are relative to the reversible hydrogen electrode.
FIG. 4 is the OER linear voltammetric scan (LSV) of the sample prepared in example 1, from which it can be seen that the current density when passing through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 250 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 326 mV. FIG. 5 is a HER Linear voltammetric scan (LSV) of the sample prepared in example 1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 63 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 112 mV.
Examples 2,
With respect to example 1, the following modifications were made: step 3), reacting for 1h at 90 ℃; the rest is equivalent to embodiment 1.
FIG. 6 is the OER linear voltammetric scan (LSV) of the sample prepared in example 2, from which it can be seen that the current density when passing through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 271 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 341 mV. FIG. 7 is a HER Linear voltammetric scan (LSV) of the sample prepared in example 2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 100 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 197 mV.
Example 3
With respect to example 1, the following modifications were made: step 3), reacting for 1h at 150 ℃; the rest is equivalent to embodiment 1.
FIG. 8 is the OER linear voltammetric scan (LSV) of the sample prepared in example 3, from which it can be seen that the current density when passing through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 294 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 365 mV. FIG. 9 is a HER Linear voltammetric scan (LSV) of the sample prepared in example 3, from which it can be seen that the current density passed by the electrode is 100mA/cm2The corresponding overpotential is 136 mV.
Comparative example 1-1, cobalt nitrate and urea were used in the same amounts, without addition of ammonium fluoride, and the remainder was identical to example 1.
The test results of the obtained material were: FIG. 10 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 1-1, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 292 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 363 mV. FIG. 11 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 1-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 72 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 147 mV.
Comparative examples 1-2, the amount of cobalt nitrate was unchanged, and the ratio of cobalt nitrate: ammonium fluoride: the molar ratio of urea is adjusted up to 1: 3: 6, the rest was identical to example 1.
The test results of the obtained material were: FIG. 12 is an OER linear voltammetric scan (LSV) of the samples prepared in comparative examples 1-2, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 300 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 379 mV. FIG. 13 is a HER Linear voltammetric scan (LSV) of the samples prepared in comparative examples 1-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 143 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 235 mV.
Comparative example 2-1, the reaction temperature in step 2) was changed from 120 ℃ to 100 ℃, and the rest was the same as example 1.
The test results of the obtained material were: FIG. 14 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 2-1, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 273 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 342 mV. FIG. 15 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 2-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 71 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 131 mV.
Comparative example 2-2, the reaction temperature in step 2) was changed from 120 ℃ to 140 ℃, and the rest was the same as in example 1.
The test results of the obtained material were: FIG. 16 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 2-2, from which the current density when the electrode passesIs 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 256 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 329 mV. FIG. 17 is a HER Linear voltammetric scan (LSV) of the samples prepared in comparative examples 2-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 71 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 128 mV.
Comparative example 3-1, the reaction time in step 2) was changed from 6h to 9h, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 18 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 3-1, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 274 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 346 mV. FIG. 19 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 3-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 87 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 170 mV.
Comparative example 3-2, the reaction time in step 2) was changed from 6h to 12h, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 20 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 3-2, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 269 mV; when the current density of the electrode passing through is 100mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 339 mV. FIG. 21 is a HER Linear voltammetric scan (LSV) of the samples prepared in comparative examples 3-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 77 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 166 mV.
Comparative example 4-1, the sodium hypophosphite powder in step 4) was changed from 300mg to 400mg, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 22 is an OER linear voltammetric scan (LS) of the sample prepared in comparative example 4-1V), it can be seen from the graph that the current density when the electrode passes through is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 262 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 341 mV. FIG. 23 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 4-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 68 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 132 mV.
Comparative example 4-2, the sodium hypophosphite powder in step 4) was changed from 300mg to 500mg, and the rest was identical to example 1.
The test results of the obtained material were: FIG. 24 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 4-2, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 254 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 340 mV. FIG. 25 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 4-2, from which it can be seen that when the electrode passes a current density of 100mA/cm2The corresponding overpotential is 136 mV.
In comparative example 5-1, the reaction time of the high-temperature oven in step 3) was changed from 1h to 3h, and the rest was the same as in example 1.
The test results of the obtained material were: FIG. 26 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 5-1, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 266 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 336 mV. FIG. 27 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 5-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 68 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 127 mV.
Comparative example 5-2, the reaction time of the high temperature oven in step 3) was changed from 1h to 5h, and the rest was the same as example 1.
The test results of the obtained material were: FIG. 28 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 5-2, from which it can be seen thatWhen the current density of the electrode passing through is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 273 mV; when the current density of the electrode passing through is 100mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 339 mV. FIG. 29 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 5-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 74 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 128 mV.
Comparative example 6-1, the concentration of the potassium permanganate solution in step 3) was changed from 0.03M to 0.01M, and the remainder was the same as in example 1.
The test results of the obtained material were: FIG. 30 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 6-1, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 278 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 346 mV. FIG. 31 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 6-1, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 73 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 128 mV.
Comparative example 6-2, the concentration of the potassium permanganate solution in step 3) was changed from 0.03M to 0.05M, and the remainder was the same as in example 1.
The test results of the obtained material were: FIG. 32 is an OER linear voltammetric scan (LSV) of the sample prepared in comparative example 6-2, from which it can be seen that when the electrode passes a current density of 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 287 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 365 mV. FIG. 33 is a HER Linear voltammetric scan (LSV) of the sample prepared in comparative example 6-2, from which it can be seen that the current density when passed through the electrode is 10mA/cm2When the voltage is higher than the threshold voltage, the corresponding overpotential is 69 mV; when the current density of the electrode passing through is 100mA/cm2The corresponding overpotential is 119 mV.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
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