CN117344344A - Chromium-doped nickel-iron sulfide array electrocatalyst prepared by foam nickel in-situ growth, and preparation method and application thereof - Google Patents
Chromium-doped nickel-iron sulfide array electrocatalyst prepared by foam nickel in-situ growth, and preparation method and application thereof Download PDFInfo
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- CN117344344A CN117344344A CN202311396653.1A CN202311396653A CN117344344A CN 117344344 A CN117344344 A CN 117344344A CN 202311396653 A CN202311396653 A CN 202311396653A CN 117344344 A CN117344344 A CN 117344344A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 239000006260 foam Substances 0.000 title claims abstract description 61
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 56
- FRWHRIRADSHXLL-UHFFFAOYSA-N iron(3+);nickel(2+);tetrasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[Fe+3].[Ni+2].[Ni+2].[Ni+2].[Ni+2] FRWHRIRADSHXLL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 239000011651 chromium Substances 0.000 claims abstract description 45
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 40
- 239000013535 sea water Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 150000001844 chromium Chemical class 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 9
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 9
- 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 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 15
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000013112 stability test Methods 0.000 claims description 6
- 150000004677 hydrates Chemical class 0.000 claims description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 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 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- IYNQBRDDQSFSRT-UHFFFAOYSA-N chromium(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IYNQBRDDQSFSRT-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052742 iron Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 238000007086 side reaction Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of electrocatalysts, and discloses a chromium-doped nickel-iron sulfide array electrocatalyst grown in situ by foam nickel, and a preparation method and application thereof, wherein the preparation method comprises the following steps: inorganic ferric salt, nickel salt, chromium salt, urea, ammonium fluoride and foam nickel are mixed, and an electrocatalyst is obtained through hydrothermal reaction; wherein the mole ratio of the chromium salt to the nickel salt is 0.25-4:4; and 2, immersing the electrocatalyst in a sodium sulfide nonahydrate solution for reaction, taking out a product, and cleaning and drying to obtain the electrocatalyst. The catalyst is in a compact 2D nano-sheet array structure, and the electron layer adsorbed on the surface is beneficial to electron transmission during the anode oxygen evolution reaction by utilizing the strong electrophilic capability of doped metal chromium, so that corrosion of chloride ions in seawater to the catalyst is more beneficial to rejection, the prepared catalyst has far beyond the electrocatalytic activity of commercial noble metal catalyst, and the catalyst still has better stability under the ultra-long-time working condition.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a chromium-doped nickel-iron sulfide array electrocatalyst grown in situ by foam nickel, and a preparation method and application thereof.
Background
Hydrogen (H) 2 ) Is regarded as an effective energy carrier, but H 2 The preparation, storage and transportation of the same are serious impediments to their large-scale use. Efficient and economical production of high purity H by electrolysis of water 2 Replacing existing traditional fossil fuels is considered to be one of the most promising technologies for alleviating global energy crisis and environmental pollution. Catalyst RuO 2 And IrO 2 The catalyst has high catalytic activity on Oxygen Evolution Reaction (OER) of electrolytic water, is widely regarded as a reference catalyst of OER reaction, but is still limited by the factors such as high price, low earth reserve, poor stability and the like in large-scale hydrogen production by electrolytic water.
On the other hand, the main progress at present has focused on the use of purified fresh water as a raw material, while less research has been conducted on catalytic electrodes for the electrolysis of seawater suitable for mass production. Therefore, the catalytic electrode with low preparation cost, excellent performance, seawater corrosion resistance and strong stability is a weight of pushing the technology of producing hydrogen by water electrolysis.
The foam nickel has larger specific surface area and good conductivity, and the nickel-iron catalyst is grown on the nickel foam in situ, so that the mechanical strength of the electrode material is improved, and the electron transmission is promoted. Meanwhile, the transition metal catalyst grown on the foam nickel in situ has low cost, unique physicochemical property, excellent electrocatalytic performance and stability, and is beneficial to the controllable synthesis of a large-area catalyst and the application of hydrogen production by water electrolysis under high current density.
The method comprises the steps of firstly, carrying out electrodeposition in a nickel metal salt electroplating solution by a dynamic hydrogen bubble template method to obtain a foam nickel composite material loaded with a layered porous nickel deposition layer; and then electrodepositing in nickel-iron metal salt electroplating solution to obtain a nickel-iron hydroxide deposition layer on the composite material, thereby obtaining the nickel-based OER electrode, and the product has lower overpotential when being used for OER reaction.
The method comprises the steps of firstly carrying out hydrothermal reaction on nickel nitrate, ferric nitrate, urea and ammonium fluoride in deionized water and foam nickel to obtain a nickel-iron hydrotalcite-like precursor material taking the foam nickel as a substrate; and then carrying out hydrothermal reaction with sodium sulfide nonahydrate solution to obtain the nickel-iron hydrotalcite-like compound/nickel-iron sulfide heterostructure OER electro-catalyst taking foam nickel as a substrate, wherein the catalyst is used as a working electrode to show high current density in the OER reaction. The catalyst has a sulfate layer formed on the surface after 2000 times of cyclic voltammetry scanning, so that the catalyst has excellent catalytic performance in alkaline brine and alkaline seawater; however, the long-time cyclic voltammetry scanning process is tedious and time-consuming. It can be seen that the catalyst without cyclic voltammetry scanning treatment had very poor stability and was essentially completely spent for about 10 hours under the conditions of 1.0M potassium hydroxide and 0.5M sodium chloride in the electrolyte.
Therefore, unlike hydrogen production by electrolysis of water in pure water, there is an important problem in seawater electrolysis, namely chloride ion corrosion, and the corrosion of metal catalysts while the side reaction of 0.5M chloride ions contained in seawater occurs at the anode, thus lowering the catalyst stability, and there is a need for improvement in the catalyst stability for use in seawater or concentrated seawater environments.
Disclosure of Invention
Aiming at the defects of poor seawater corrosion resistance, low stability and the like of a transition metal-based electrocatalyst in the prior art, the invention provides the chromium-doped nickel iron sulfide array electrocatalyst grown on foam nickel in situ, which is prepared by mixing a transition metal chromium species with Lewis acidity after synthesizing a bimetallic sulfide with a 2D nano array structure, reduces the overpotential of the electrocatalytic OER, improves the electrocatalytic performance, simultaneously increases the capability of resisting chloride ion corrosion, and improves the long-term stability of the electrocatalyst in electrolytic seawater.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the chromium-doped nickel iron sulfide array electrocatalyst with foam nickel grown in situ comprises the following steps:
step 1, mixing inorganic ferric salt, inorganic nickel salt, inorganic chromium salt, urea and ammonium fluoride in deionized water, adding pretreated foam nickel into the solution, and obtaining a chromium-doped ferronickel array electrocatalyst for in-situ growth of the foam nickel through hydrothermal reaction; wherein the mol ratio of the inorganic chromium salt to the inorganic nickel salt is 0.25-4:4;
and 2, immersing the chromium-doped ferronickel array electrocatalyst in sodium sulfide nonahydrate solution, taking out a product after the immersion reaction, and washing and drying to obtain the chromium-doped ferronickel sulfide array electrocatalyst.
According to the invention, foam nickel is used as a catalyst carrier, a bimetal nano-array growing on the foam nickel in situ is obtained through the hydrothermal reaction of nickel salt and ferric salt, a certain amount of chromium salt is added in the process, and as the transition metal chromium has stronger electrophilic capability, the electron transmission capability of the nickel-iron nano-array electrocatalyst is improved, the resistance to chloride ion corrosion is enhanced, and the chromium doped nickel-iron array electrocatalyst growing on the foam nickel in situ is obtained. Then, the nickel-iron array electrocatalyst is subjected to chemical impregnation treatment by sodium sulfide solution, so that the connection capability between different metals of the nickel-iron array electrocatalyst is more stable, the overall strength and heat resistance are improved, and the chemical corrosion resistance is also stronger.
The metal chromium has stronger electrophilic capability, so that on one hand, the chlorine ion corrosion resistance of the electrocatalyst can be improved, on the other hand, the catalyst catalytic performance can be further improved due to the good electron transmission capability, the process of the electrolytic water OER reaction can be accelerated, the chlorine ion corrosion resistance in simulated seawater is optimized, and the catalytic activity and stability of the catalyst are greatly improved. After the metal chromium is doped, the electron distribution condition around the active site nickel and iron can be influenced by the outer layer orbital electrons of the chromium, and the nano-array formed by the three metals can play a synergistic effect, so that the catalyst overall shows better performance and stability in OER reaction.
The inorganic ferric salt comprises one or more of ferric nitrate, ferric chloride, ferric sulfate and hydrate thereof;
the inorganic nickel salt comprises one or more of nickel nitrate, nickel chloride, nickel sulfate and hydrates thereof;
the inorganic chromium salt comprises one or more of chromium nitrate, chromium chloride, chromium sulfate and hydrates thereof.
The preparation process of the pretreated foam nickel comprises the following steps: and ultrasonically washing the foam nickel by hydrochloric acid, ethanol and deionized water, and drying to obtain the pretreated foam nickel.
The transition metal sulfide exhibits good water-electrolysis OER reactivity due to its outstanding electronic structure and good conductivity. Due to the synergistic effect between the two metal cations, binary transition metal catalysts have better electrochemical activity than single metal catalysts. The ferronickel bimetallic is adopted in the invention, based on the fact that the ferronickel bimetallic has better water dissociation performance compared with other transition metals.
Preferably, the inorganic nickel salt and inorganic iron salt are in a molar ratio of 4:1 to 4; the proportion of the ferronickel metal influences the dispersion condition of the nano-array formed in the catalyst, the nano-array in the catalyst obtained by the proportion has proper dispersion tightness, a large number of active sites and large specific surface area, and the electrolytic water OER activity of the catalyst is excellent.
4 of the inorganic nickel salts, urea and ammonium fluoride: 40-60: 15-25;
the dosage of chromium is very critical in the invention, and the excessive chromium can cover the original active site of the catalyst, thereby affecting the OER activity of the catalyst in electrolytic water, but the dosage is too small to realize the effect of resisting chloride ion corrosion, and affecting the long-term stability of the catalyst in seawater.
The hydrothermal reaction temperature in the step 1 is 100-180 ℃ and the reaction time is 4-8 h. Preferably, the temperature of the hydrothermal reaction is 110-130 ℃ and the reaction time is 5-7 h. The adoption of a moderate temperature prevents the agglomeration of chromium metal at a high temperature, thereby affecting the growth distribution of the nano array.
Still more preferably, the hydrothermal reaction temperature is 120℃and the reaction time is 6 hours.
In the step 2, the molar concentration of the sodium sulfide nonahydrate solution is 0.03-0.09M, the temperature of the dipping reaction is 20-80 ℃ and the time is 1-3 h. Preferably, the concentration of the sodium sulfide nonahydrate solution in the impregnation reaction is 0.05M-0.07M, the impregnation temperature is 50-70 ℃, and the reaction time is 1.5-2.5 h.
The method adopts moderate impregnation concentration, temperature and time to regulate the vulcanization degree of the metal oxide, and the electronic structure between metals can be regulated in the vulcanization process, so that the overall conductivity is improved, and the catalyst is beneficial to the water electrolysis OER under the condition of high current density; however, too high a degree of sulfidation may result in increased metal crystallinity, thereby affecting the oxygen evolution performance of the nanoarray catalyst.
Still more preferably, the impregnation reaction has a sodium sulfide nonahydrate concentration of 0.06M, an impregnation temperature of 60℃and a reaction time of 2 hours.
Preferably, the molar ratio of the inorganic chromium salt to the inorganic nickel salt is 0.75-2: 4, the chromium doping amount of the catalyst synthesized in the range is moderate, and the OER performance and the stability thereof in simulated seawater are all optimal; when the doping amount is too low, the electrophilic capability of the chromium with stronger is not fully embodied, and the electron transmission capability and the chloride ion corrosion resistance of the whole catalyst are not obviously improved; too high doping levels can cover the original active sites on the catalyst surface, resulting in reduced catalytic activity.
The invention also provides a chromium-doped nickel-iron sulfide array electrocatalyst prepared by the preparation method and grown in situ, wherein the chromium-doped nickel-iron sulfide array electrocatalyst has a 2D nano-sheet array structure, and the chromium doping amount is 1-10wt%, preferably 4-6wt%.
The invention also provides application of the foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst in catalytic oxygen evolution in natural seawater or alkaline seawater.
The concentration of chloride ion in the natural seawater or alkaline seawater is above 0.5M, such as 0.5M, 1M, 2M, 6M, etc.
Preferably, in the water-in-anode OER reaction, a three-electrode system is adopted, in particular to an Hg/HgO electrode is used as a reference electrode, a carbon rod is used as a counter electrode, the chromium-doped nickel-iron sulfide array electrocatalyst grown on foam nickel in situ provided by the invention is used as a working electrode, and the electrolyte contains 0.5M chloride ions.
Under the condition that the current is 0.1A and the electrolyte is a mixed solution of 1.0M KOH and 0.5M NaCl, the potential of the catalyst is reduced to be within 15mV after 200h stability test;
furthermore, the chromium doped nickel iron sulfide array electrocatalyst is used as a working electrode, and under the condition that the electrolyte is a mixed solution of 1.0M KOH and 2M NaCl at the current of 0.1A, the potential of the catalyst is reduced to be within 20mV after 100h stability test, so that the stability is very excellent. The chromium doped nickel-iron sulfide array electrocatalyst grown on the foam nickel in situ provided by the invention has the advantages that the transition metal chromium is doped on the surface of the nickel-iron nanosheet array, so that the electrode material shows good conductivity and stability, and meanwhile, the chromium doped nickel-iron nanosheet array has tighter arrangement and higher specific surface area, is beneficial to the dispersion of catalytic active sites, and further increases the electrocatalytic activity.
The catalyst is prepared by taking foam nickel as a carrier, and the chromium-doped nickel-iron sulfide nano-arrays are uniformly distributed on the surface of the foam nickel. The nanometer has larger specific surface area and more active sites, is convenient for electrolyte permeation and ion diffusion, and is favorable for oxygen generation and precipitation; the doped metal chromium has good synergistic effect on the double sites of nickel and iron, accelerates the reaction process, reduces the overpotential of the doped metal chromium in OER reaction, and improves the overall reaction of the catalyst.
Because chromium ions are Lewis acid, the chromium ions have stronger electrophilic capability and are favorable for electron transmission; meanwhile, the adsorbed electrons can form an electron layer on the surface of the catalyst, and the electronegativity of the adsorbed electrons can repel attack of chloride ions, so that the effect of improving the selectivity and enhancing the stability of the electrolytic water OER in simulated seawater is achieved, and the effect of multi-angle enhancement is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) By one-step hydrothermal and impregnationThe chromium doped nickel iron sulfide array electrocatalyst grown on the foam nickel in situ is nano, the chromium ion doping is utilized to improve the corrosion resistance of the catalyst to chloride ions, the electron transmission capacity of the catalyst is improved, and the nickel iron sulfide nano array efficient water dissociation, larger specific surface area and more exposed active sites are combined, so that the electron transfer and the intermediate adsorption and desorption in the reaction process are facilitated, the array structure is favorable for faster precipitation of product gas, and the reaction of electrolyte and the catalyst surface active sites is accelerated, so that the catalyst shows more commercial RuO 2 The OER performance of the catalyst for the electrolytic water has great significance for realizing the hydrogen production of the electrolytic seawater.
(2) The chromium doped nickel iron sulfide array electrocatalyst grown on the foam nickel in situ provided by the invention has high-efficiency electrocatalytic activity and ultra-long-time catalytic stability in simulating seawater, high-concentration seawater and the like, and provides great application possibility for development and utilization of hydrogen energy prepared by electrolyzing seawater.
(3) The chromium doped nickel iron sulfide array electrocatalyst grown on the foam nickel in situ provided by the invention adopts relatively cheap, environment-friendly, rich in reserves and high in safety transition metal iron, nickel and chromium, and the electrolytic water OER catalyst on the foam nickel substrate is obtained by a simple preparation method.
Drawings
FIG. 1 is a SEM image of the catalyst Cr-NiFeS/NF prepared in example 1.
FIG. 2 is an X-ray diffraction XRD pattern of the catalyst Cr-NiFeS/NF prepared in example 1.
FIG. 3 is a graph showing the polarization of the chromium doped catalysts Cr-NiFeS/NF prepared in examples 1-3 in the application example to simulate the oxygen evolution reaction of seawater.
FIG. 4 is a graph showing the polarization of the catalyst Cr-NiFeS/NF prepared in example 1 in application example for electrolytically simulating seawater and high concentration seawater oxygen evolution reaction.
FIG. 5 is a graph showing the polarization curves of the catalysts prepared in example 1 and comparative examples 1 to 4 in the application example for electrolytically simulating the oxygen evolution reaction of seawater.
FIG. 6 is a schematic illustration of example 1 and a commercial catalyst RuO 2 In the application example, the polarization curve diagram of the seawater oxygen evolution reaction is simulated in an electrolysis mode.
FIG. 7 is a graph showing the voltage change with time under constant current for the catalyst Cr-NiFeS/NF prepared in example 1 to simulate the seawater oxygen evolution reaction.
FIG. 8 is a graph showing the voltage change with time under constant current for simulating the oxygen evolution reaction of high concentration seawater by the electrolysis of Cr-NiFeS/NF catalyst prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Example 1
(1) Cutting untreated foam nickel into small pieces with the length of 3cm multiplied by 4cm, sequentially ultrasonically washing the small pieces in 1.0M hydrochloric acid solution, absolute ethyl alcohol and deionized water for 15min, removing oxides and impurities on the surface of the foam nickel, and drying the foam nickel in a vacuum oven at the temperature of 60 ℃ for later use;
(2) 1.16g of nickel nitrate hexahydrate solid particles, 1.62g of ferric nitrate nonahydrate solid particles and 0.4g of chromium nitrate hexahydrate solid particles are weighed, dissolved in 60mL of deionized water and evenly stirred; 0.74g of ammonium fluoride and 3.18g of urea were weighed, added to the above-mentioned uniform mixed solution, and stirred for 30 minutes to obtain a uniform solution.
Transferring the obtained uniform mixed solution into a hydrothermal reaction kettle, putting a piece of treated foam nickel into the solution, putting the solution into an oven for hydrothermal reaction after the foam nickel is completely immersed in the solution, setting the hydrothermal temperature to be 120 ℃, heating for 6 hours, taking out the foam nickel after the reaction is finished, centrifugally washing the foam nickel by water and ethanol for three times, and vacuum drying the obtained product at 60 ℃ to obtain the chromium-doped nickel-iron array electrocatalyst growing on the foam nickel in situ;
(3) Weighing 0.36g of sodium sulfide nonahydrate, dissolving in 25mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain a uniformly dispersed solution; cutting out 1X 3cm from the chromium doped ferronickel array electrocatalyst grown on the foam nickel in situ -2 Then immersing in sodium sulfide solution, standing in an oven at 60 ℃ for 2 hours, washing with deionized water for three times, and vacuum drying the obtained product at 60 ℃ to obtain the chromium doped nickel iron sulfide array electrocatalyst grown on foam nickel in situ, which is recorded as Cr-NiFeS/NF, wherein the chromium doping amount is 5wt%.
The prepared catalyst was observed for macroscopic morphology by scanning electron microscope SEM, and the results are shown in fig. 1. It can be seen from fig. 1 that the nickel-iron array grows on the surface of the foam nickel, forming a uniform nano-array structure.
XRD of the chromium doped nickel iron sulfide array catalyst grown in situ on foamed nickel prepared in this example is shown in FIG. 2, and it can be seen that the catalyst mainly contains diffraction peaks of crystalline NiFe (JCPDS No. 49-0188) in addition to the three characteristic diffraction peaks of the foamed nickel substrate. No significant diffraction peak was observed due to the low Cr content in the catalyst.
Examples 2 to 3
According to the preparation process of example 1, the addition amounts of 0.1g and 1.6g were carried out during step (2) on the solid particles of chromium nitrate hexahydrate in the solution of the first step, the samples were designated Cr, respectively 0.25 NiFeS/NF and Cr 4 NiFeS/NF, chromium doping levels of 1wt% and 10wt%, respectively.
Comparative example 1
According to the preparation process of example 1, no solid particles of chromium nitrate hexahydrate were added, and an in-situ growth of an iron nickel sulfide array electrocatalyst on nickel foam, designated NiFeS/NF, was obtained.
The elemental compositions and contents of the catalysts prepared in example 1 and comparative example 1, as measured by EDS spectrometer, are shown in table 1, it can be seen that the Cr to Fe content ratio is close to the feed ratio; in Table 1, the Cr content of the comparative example NiFeS/NF was close to 0, and the trace amount was possibly caused by the interference of other elements.
TABLE 1 composition of the catalysts Cr-NiFeS/NF and NiFeS/NF element prepared in example 1 and comparative example 1
Comparative example 2
The preparation process of example 1 was followed except that the chromium salt in step (2) was replaced with a cobalt salt to obtain a cobalt doped nickel iron sulfide array electrocatalyst grown in situ on the foam nickel, designated Co-NiFeS/NF.
Comparative example 3
The preparation process of example 1 was followed except that in step (2) the chromium salt was replaced with a manganese salt to obtain a manganese doped nickel iron sulfide array electrocatalyst grown in situ on the nickel foam, designated Mn-NiFeS/NF.
Comparative example 4
The preparation process of example 1 was followed except that in step (2) the nickel salt was replaced with a tin salt to obtain a tin-doped nickel iron sulfide array electrocatalyst grown in situ on the nickel foam, designated Sn-NiFeS/NF.
Application example
(1) Using a three-electrode system, using the catalysts prepared in examples 1-3 or comparative examples 1-4 as working electrodes, using a carbon rod as a counter electrode, using Hg/HgO as a reference electrode, and using 1.0M KOH+0.5M NaCl as electrolyte;
(2) CV activation: nitrogen was introduced into the electrolyte for 30min before testing using the Shanghai Chenhua CHI 760E electrochemical workstation. The CV program is adopted, the test interval is 1.1-2.0V vs. RHE, and the sweeping speed is 50 mV.s -1 The electrode reaches a stable state after 40 circles of circulation.
(3) LSV test: the catalysts prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to a Linear Sweep Voltammetry (LSV) test. After the sample is subjected to CV activation, the workstation switching program is changed into an LSV program, the test interval is 1.1-2.0V vs. RHE, and the sample is scannedThe speed is 5 mV.s -1 The overpotential was 1.23V and 100mA cm relative to the reversible hydrogen electrode -2 The difference in potential is measured.
The results of examples 1 to 3 are shown in fig. 3, wherein the material in example 1 is labeled as Cr1-NiFeS/NF in the figure, and it is seen from the figure that the catalyst has the best electrocatalytic performance when the adding amount of the chromium salt is 1mmol, because the synthesized nickel-iron nano-array is not compact enough, sparse, and has fewer active sites, and the original nickel-iron nano-array surface is covered when the adding amount of the chromium salt is too high, which is unfavorable for the exposure of the active sites. Therefore, when the addition amount of the chromium salt is 1mmol, the synthesized nano-array is uniformly arranged, and the catalyst active component has good dispersibility and excellent electrocatalytic performance.
Example 1 test results in simulated seawater and simulated seawater of high chloride concentration As shown in FIG. 4, in simulated seawater electrolyte, the Cr-NiFeS/NF catalyst was used at 100mA cm -2 Is only 260mV; in the sea water electrolyte simulating high chloride ion concentration, the Cr-NiFeS/NF catalyst is in the range of 100mA cm -2 Is only 300mV. Indicating that the catalyst has excellent catalytic activity under different environments.
The polarization graphs of the Cr-NiFeS/NF catalyst and the reactions of NiFeS/NF, co-NiFeS/NF, mn-NiFeS/NF and Sn-NiFeS/NF (example 1 and comparative examples 1-4) in the mixed solution of 1.0M KOH and 0.5M NaCl are shown in FIG. 5, and it can be seen from FIG. 5 that in the simulated seawater electrolyte, the catalytic effect of the Cr-NiFeS/NF catalyst is significantly better than that of nickel-iron sulfide arrays or nickel-iron sulfide array catalysts doped with other transition metals (cobalt, manganese and tin), even better than that of commercial RuO 2 The performance of the catalyst (overpotential 410mV, see fig. 6).
Stability test of the catalyst prepared in example 1
After CV activation, the switching procedure was ISTEP procedure, the current was set to 0.1A, the time was set to 750000s, and the electrolyte was a mixed solution of 1.0M KOH and 0.5M NaCl. As shown in fig. 7, the potential of the chromium doped nickel iron sulfide array electrocatalyst grown in situ on foamed nickel was reduced by about 15mV after the stability test for more than 200 hours, demonstrating its excellent catalytic stability and resistance to chloride corrosion for an extra time.
After CV activation, the switching procedure was an ISTEP procedure, the current was set to 0.1A, the time was set to 400000s, and the electrolyte was a 1.0M KOH and 2M NaCl mixed solution. The test results are shown in fig. 8, and the chromium doped nickel iron sulfide array electrocatalyst grown on the foam nickel in situ has the stability tested for more than 100 hours in simulated seawater containing high concentration of chloride ions, and the potential is reduced by about 20mV, so that the electrocatalyst still has good catalytic stability and chloride ion corrosion resistance under the environment with higher chloride content.
Claims (10)
1. The preparation method of the chromium-doped nickel iron sulfide array electrocatalyst with foam nickel grown in situ is characterized by comprising the following steps:
step 1, mixing inorganic ferric salt, inorganic nickel salt, inorganic chromium salt, urea and ammonium fluoride in deionized water, adding pretreated foam nickel into the solution, and obtaining a chromium-doped ferronickel array electrocatalyst for in-situ growth of the foam nickel through hydrothermal reaction; wherein the mol ratio of the inorganic chromium salt to the inorganic nickel salt is 0.25-4:4;
and 2, immersing the chromium-doped ferronickel array electrocatalyst in sodium sulfide nonahydrate solution, taking out a product after the immersion reaction, and washing and drying to obtain the chromium-doped ferronickel sulfide array electrocatalyst.
2. The method for preparing a foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst according to claim 1, wherein the inorganic iron salt comprises one or more of iron nitrate, iron chloride, iron sulfate, and hydrates thereof;
and/or the inorganic nickel salt comprises one or more of nickel nitrate, nickel chloride, nickel sulfate and hydrates thereof;
and/or the inorganic chromium salt comprises one or more of chromium nitrate, chromium chloride, chromium sulfate and hydrates thereof;
and/or, the preparation process of the pretreated foam nickel comprises the following steps: and ultrasonically washing the foam nickel by hydrochloric acid, ethanol and deionized water, and drying to obtain the pretreated foam nickel.
3. The method for preparing the foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst according to claim 1, wherein the molar ratio of the inorganic nickel salt to the inorganic iron salt is 4:1 to 4;
the molar ratio of the inorganic nickel salt to the urea to the ammonium fluoride is 4: 40-60: 15-25.
4. The method for preparing the foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst according to claim 1, wherein the hydrothermal reaction temperature in step 1 is 100-180 ℃ and the reaction time is 4-8 hours.
5. The method for preparing the foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst according to claim 1, wherein the molar concentration of the sodium sulfide nonahydrate solution in step 2 is 0.03 to 0.09M.
6. The method for preparing the foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst according to claim 1, wherein the temperature of the impregnation reaction in step 2 is 20-80 ℃ for 1-3 hours.
7. The method for preparing the foam nickel in-situ grown chromium doped nickel iron sulfide array electrocatalyst according to claim 1, wherein the molar ratio of the inorganic chromium salt to the inorganic nickel salt is 0.75-2: 4.
8. the foam nickel in-situ grown chromium-doped nickel-iron sulfide array electrocatalyst according to any one of claims 1 to 7, wherein the chromium doping amount in the chromium-doped nickel-iron sulfide array electrocatalyst is 1 to 10wt%.
9. The use of a chromium doped nickel iron sulfide array electrocatalyst grown in situ with nickel foam according to claim 8 for catalytic oxygen evolution in natural or alkaline seawater.
10. The use according to claim 9, wherein the chromium doped nickel iron sulfide array electrocatalyst is used as a working electrode, and the potential of the catalyst is reduced to within 15mV after 200h stability test under the condition that the electrolyte is a mixed solution of 1.0M KOH and 0.5M NaCl at a current of 0.1A;
the chromium-doped nickel-iron sulfide array electrocatalyst is used as a working electrode, and the potential of the catalyst is reduced within 20mV after 100h stability test under the condition that the electrolyte is a mixed solution of 1.0M KOH and 2M NaCl at the current of 0.1A.
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