CN111111707B - Selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and preparation method and application thereof - Google Patents
Selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and preparation method and application thereof Download PDFInfo
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- CN111111707B CN111111707B CN201911420523.0A CN201911420523A CN111111707B CN 111111707 B CN111111707 B CN 111111707B CN 201911420523 A CN201911420523 A CN 201911420523A CN 111111707 B CN111111707 B CN 111111707B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 89
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229910001691 hercynite Inorganic materials 0.000 title claims abstract description 63
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010935 stainless steel Substances 0.000 claims abstract description 46
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 19
- 239000011029 spinel Substances 0.000 claims abstract description 19
- 239000002135 nanosheet Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 239000011669 selenium Substances 0.000 claims description 20
- 229910052711 selenium Inorganic materials 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000012670 alkaline solution Substances 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 10
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- RBRLCUAPGJEAOP-UHFFFAOYSA-M sodium selanide Chemical compound [Na+].[SeH-] RBRLCUAPGJEAOP-UHFFFAOYSA-M 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 16
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 abstract 2
- 238000001291 vacuum drying Methods 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 14
- 229940091258 selenium supplement Drugs 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 239000010963 304 stainless steel Substances 0.000 description 8
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 8
- NLZOGIZKBBJWPB-UHFFFAOYSA-N [Na].[SeH2] Chemical compound [Na].[SeH2] NLZOGIZKBBJWPB-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001075 voltammogram Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- RVIXKDRPFPUUOO-UHFFFAOYSA-N dimethylselenide Chemical compound C[Se]C RVIXKDRPFPUUOO-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- OZCVYQHMJCGOOQ-UHFFFAOYSA-H [Se](=O)([O-])[O-].[Ce+3].[Se](=O)([O-])[O-].[Se](=O)([O-])[O-].[Ce+3] Chemical compound [Se](=O)([O-])[O-].[Ce+3].[Se](=O)([O-])[O-].[Se](=O)([O-])[O-].[Ce+3] OZCVYQHMJCGOOQ-UHFFFAOYSA-H 0.000 description 1
- WTKUDAMSULHEKV-UHFFFAOYSA-N [Se](C#N)C#N.[K] Chemical compound [Se](C#N)C#N.[K] WTKUDAMSULHEKV-UHFFFAOYSA-N 0.000 description 1
- HDRGIEIPCNKUID-UHFFFAOYSA-J [Zr+4].[O-][Se]([O-])=O.[O-][Se]([O-])=O Chemical compound [Zr+4].[O-][Se]([O-])=O.[O-][Se]([O-])=O HDRGIEIPCNKUID-UHFFFAOYSA-J 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RGZGHMSJVAQDQO-UHFFFAOYSA-L copper;selenate Chemical compound [Cu+2].[O-][Se]([O-])(=O)=O RGZGHMSJVAQDQO-UHFFFAOYSA-L 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- NRUPVVPBPCPMPJ-UHFFFAOYSA-N cyano selenocyanate Chemical compound N#C[Se]C#N NRUPVVPBPCPMPJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YPORSSIFOTVJLV-UHFFFAOYSA-H dialuminum;triselenite Chemical compound [Al+3].[Al+3].[O-][Se]([O-])=O.[O-][Se]([O-])=O.[O-][Se]([O-])=O YPORSSIFOTVJLV-UHFFFAOYSA-H 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 transition metal chalcogenide Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and a preparation method and application thereof. The microstructure of the composite electrocatalyst material is that selenium-doped nickel-iron spinel nano-particles and hydroxyl nickel oxide nano-sheets are mutually connected, the diameter of the selenium-doped nickel-iron spinel nano-particles is 200-400 nm, the thickness of the hydroxyl nickel oxide nano-sheets is 8-15 nm, and the transverse length is 1-3 mu m. According to the invention, stainless steel is used as a raw material, a nickel hercynite/nickel oxyhydroxide compound precursor grows in situ on the surface of the stainless steel, and then the obtained precursor is subjected to accurate selenization under a hydrothermal condition, so that the purpose of preparing an accurate selenium-doped nickel hercynite/nickel oxyhydroxide electrocatalyst is achieved. The preparation method has mild conditions, simple process and low requirement on equipment; the obtained material is used for water decomposition reaction, and has low overpotential, good stability and other electrochemical properties.
Description
Technical Field
The invention relates to a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and a preparation method and application thereof, belonging to the technical field of electrochemistry.
Background
The rapid increase in carbon dioxide emissions has raised concerns about global warming and has also raised an urgent need for sustainable clean energy. Among various clean energy sources, hydrogen is considered as one of the most promising alternatives to fossil fuels because of its advantages such as excellent energy density and environmental friendliness.
Among various methods for producing hydrogen, electrocatalytic Hydrogen Evolution Reaction (HER) in alkaline electrolyte has attracted much attention due to its high production safety and product purity. The key problem of the electrochemical water splitting reaction is high energy consumption, and the water electrolysis reaction still needs higher overpotential no matter the anodic Oxygen Evolution Reaction (OER) or the cathodic Hydrogen Evolution Reaction (HER), which greatly limits the water electrolysis efficiency. In order to reduce the overpotential of the water electrolysis reaction and reduce the consumption of electric energy, an electro-catalyst with high activity is explored to be an effective way for improving the water electrolysis efficiency and reducing the overpotential of oxygen generation. In the electrocatalytic decomposition of water, the anodic Oxygen Evolution Reaction (OER) is kinetically more difficult than the Hydrogen Evolution Reaction (HER) since it involves a slow four-electron process, which results in a drastic decrease in the efficiency of the water-splitting hydrogen production process. Therefore, the development of the anode oxygen evolution reaction catalyst with high activity and the reduction of the overpotential of the anode oxygen evolution reaction have very important significance for improving the hydrogen production efficiency of the electrolyzed water.
At present, noble metal based materials (IrO)2Or RuO2Etc.) catalysts are still considered to be the most advanced Oxygen Evolution Reaction (OER) electrocatalysts, but their scarcity and poor stability of materials has hindered their large-scale practical application. Therefore, there is a need to develop a cost-effective and sustainable alternative with electrocatalytic activity comparable to noble metal-based catalysts and abundant on earth. Great efforts have been made to find inexpensive alternatives in transition metal alloys, oxides, hydroxides, selenides and even chalcogenides. In recent years, sulfidation or selenization of transition metal oxides and hydroxides has been found to be an effective method for creating highly active sites in electrochemical processes, and a number of electrocatalysts have been reported. For example, Chinese patent document CN106430122A provides a NiSe2The invention discloses a transition metal chalcogenide nano-sheet, a preparation method and application thereof, wherein a nickel source compound and ammonia water are used as raw materials, and Ni (OH) is grown on a substrate in a heat preservation manner2Nanosheet, then Se displacement to obtain NiSe2Transition metal chalcogenide nanoplatelets. Chinese patent document CN110314690A discloses a bimetallic sulfide Ni with heterogeneous interface coupling3S2The preparation method of the/FeS composite material comprises the following steps: preparing a Ni and Fe-containing double metal hydroxide precursor by an electrodeposition methodAnd performing in-situ vulcanization treatment to form the dual-phase Ni and Fe sulfide composite material with a heterogeneous interface. However, the above catalysts have disadvantages of high overpotential or poor stability and complicated preparation process, so that the search for a stable and efficient catalyst is urgent.
Therefore, the preparation of an efficient and stable transition metal-based catalyst remains a very challenging issue. At present, no report is found on a method for accurately synthesizing a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material, a preparation method and application thereof. The synthesis method is simple, and the obtained electrocatalyst material is in a shape that nano particles and nano sheets are connected with each other; the obtained electrocatalyst material can be applied to the electrolytic water oxygen evolution reaction and has lower overpotential and higher chemical stability.
The technical scheme of the invention is as follows:
a selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material is characterized in that the micro-morphology of the composite electrocatalyst material is that selenium-doped nickel-iron spinel nano-particles and nickel oxyhydroxide nano-sheets are mutually connected, the diameter of the selenium-doped nickel-iron spinel nano-particles is 200-400 nm, the thickness of the nickel oxyhydroxide nano-sheets is 8-15 nm, and the transverse length is 1-3 mu m; the composite electrocatalyst material is prepared by carrying out hydrothermal alkali treatment on the surface of stainless steel to grow a precursor containing nickel hercynite nanoparticles/nickel oxyhydroxide nanosheets in situ, and then carrying out accurate selenization on the obtained precursor by adopting a selenium source.
According to the invention, preferably, the stainless steel is one of 200 series, 300 series, 400 series, 500 series and 600 series;
preferably, the thickness of the stainless steel is 0.01-5 mm.
According to the invention, the alkaline solution of the hydrothermal alkali treatment is preferably a potassium hydroxide solution, and the concentration is 1-20 mol/L.
According to the present invention, preferably, the selenium source is one of sodium hydroselenide solution, selenourea, zirconium selenite, cerium selenite, copper selenate, selenic acid, selenium powder-hydrazine hydrate solution, selenium powder-sodium borohydride solution, hydrogen selenide, sodium selenite, dimethyl selenide, potassium selenocyanide, dimethyl selenium, aluminum selenite, and selenium cyanide; further preferably one of a sodium hydrogen selenide solution, a selenium powder-hydrazine hydrate solution, and a selenium powder-sodium borohydride solution.
According to the invention, the preparation method of the sodium hydrogen selenide solution is the prior art, and can also be obtained by adopting the following preparation method:
in N2Adding selenium powder into NaBH under atmosphere4Stirring at room temperature until selenium powder is completely dissolved in the deionized water to obtain a sodium hydroselenide solution, wherein the selenium powder and NaBH4The mass ratio of the sodium hydrogen selenide solution to the organic solvent is 1: 1-3, and the concentration of the obtained sodium hydrogen selenide solution is 2-200 mmol/L.
According to the invention, the preparation method of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
(1) carrying out hydrothermal reaction on the pretreated stainless steel and an alkaline solution at the temperature of 60-220 ℃ for 6-90 h, and washing and drying after the reaction is finished to obtain a nickel-iron spinel/nickel oxyhydroxide precursor;
(2) carrying out hydrothermal precision selenization on the nickel hercynite/nickel oxyhydroxide precursor obtained in the step (1) and a selenium source solution, and after the reaction is finished, washing and drying to obtain the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
According to the preparation method of the present invention, preferably, the pretreatment step in the step (1) is: respectively ultrasonically cleaning stainless steel for 30min by sequentially using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water to remove organic pollutants on the surface and oxides on the surface, and then carrying out vacuum drying for 0.5-120 h at 25-150 ℃; further preferably, the vacuum drying temperature is 60 ℃ and the vacuum drying time is 24 h.
According to the production method of the present invention, it is preferable that the body of the alkaline solution described in the step (1)The ratio of the product to the area of the stainless steel is 4-30: 1mL/cm2More preferably 10 to 20:1mL/cm2。
According to the preparation method of the present invention, preferably, the washing in step (1) is washing with deionized water and absolute ethyl alcohol in sequence.
According to the preparation method of the invention, preferably, the drying in the step (1) is vacuum drying at 25-150 ℃ for 0.5-120 h; further preferably, the drying is vacuum drying at 90 ℃ for 24 h.
According to the preparation method provided by the invention, preferably, the concentration of selenium in the selenium source solution in the step (2) is 2-200 mmol/L;
preferably, the ratio of the volume of the selenium source solution to the area of the stainless steel is 3-30: 1mL/cm2More preferably 10 to 20:1mL/cm2。
According to the preparation method provided by the invention, preferably, the temperature of the hydrothermal precision selenization in the step (2) is 20-240 ℃, and further preferably 120-220 ℃; the hydrothermal accurate selenization time is 0.5-120 h, and the optimal time is 12-48 h.
According to the preparation method of the present invention, preferably, the washing in the step (2) is washing with deionized water and absolute ethyl alcohol in sequence.
According to the preparation method of the invention, preferably, the drying in the step (2) is vacuum drying at 25-150 ℃ for 0.5-120 h; further preferably, the drying is vacuum drying at 90 ℃ for 24 h.
According to the invention, the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material is applied to alkaline aqueous solution electrolysis water oxygen evolution as an anode electrocatalyst.
According to the invention, the application of the electrocatalyst as an anode in the electrolysis of water in an alkaline aqueous solution for oxygen evolution can be carried out according to the prior art; preferably, the step of applying the anode electrocatalyst to the alkaline aqueous solution for water electrolysis to generate oxygen comprises the following steps:
(1) preparation of electrolytic solutions
Weighing 56.1g of potassium hydroxide, dissolving the potassium hydroxide in a beaker filled with 400mL of distilled water, stirring and dissolving for 10min under magnetic stirring to form a uniform and transparent solution, then pouring the solution into a 1000mL volumetric flask, fixing the volume to the scale mark of the volumetric flask to form a 1mol/L potassium hydroxide solution, taking the uniform 100mL potassium hydroxide solution, introducing oxygen for half an hour to remove other dissolved gases in the solution to form an oxygen-saturated potassium hydroxide solution;
(2) oxygen evolution by electrolysis of water
And (3) building a three-electrode system in the electrolytic cell, and performing electrochemical water decomposition by using the oxygen-saturated potassium hydroxide solution as an electrolyte solution, the synthesized selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material as a working electrode, the double-salt bridge silver/silver chloride electrode as a reference electrode and the platinum sheet as a counter electrode.
The invention has the following technical characteristics and beneficial effects:
1. the preparation method of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material is simple, a precursor of nickel hercynite nanoparticles/nickel oxyhydroxide nanosheets can be grown only by carrying out simple hydrothermal alkali treatment reaction, then the precursor is subjected to hydrothermal selenization to obtain the selenium-doped nickel hercynite nanoparticles/nickel oxyhydroxide nanosheets composite electrocatalyst material, the concentration of reactants, the reaction time, the reaction temperature and the like are controlled, and the purpose of accurate selenization can be achieved, so that the catalyst material with excellent final performance is prepared; the synthesis condition of the invention is mild, the energy consumption is low, the process is simple, the requirement on equipment is low, and the cost is low; the hydrothermal accurate selenizing method is also suitable for other metal oxides, and can hydrothermally generate the accurately selenized selenium-doped metal oxide electrocatalyst under the conditions of proper reactant concentration, reaction time and reaction temperature.
2. The invention selects cheap stainless steel with excellent conductivity and three-dimensional framework as the current collector and reaction raw materials, the used raw materials have larger content in the earth, wide sources, large-scale production in industry and low cost; and the obtained selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material directly grows on the surface of the stainless steel, and the synthesized catalyst does not need to be attached to the surface of a support electrode, so that the process is simplified and the production cost is reduced.
3. The composite electrocatalyst material prepared on the stainless steel has multi-component components, is a selenium-doped nickel hercynite nanoparticle and nickel oxyhydroxide nanosheet composite material, has a stable three-dimensional structure and a higher surface area, can improve the mass transfer capacity of the catalyst due to the formation of the three-dimensional heterostructure, is beneficial to the exposure of electrochemical active sites, increases the electrochemical active area of the material, increases the hydrophilicity between the surface of the electrocatalyst and electrolyte, can be better adsorbed with water molecules, can more quickly remove gas, and thus improves the catalytic activity of the catalyst. The selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in situ on stainless steel has the current density of 10mA/cm2The overpotential is only 182 mV; the stability is measured by a chronoamperometry method at a value corresponding to 10mA/cm2And 100mA/cm2The catalytic activity can be respectively maintained above 500h and 300h under the voltage, and the catalyst has lower overpotential and higher stability.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of 304 stainless steel used in the examples.
Fig. 2 is an X-ray diffraction (XRD) spectrum of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in example 1.
Fig. 3 is a Raman spectrum of a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in example 1.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in example 1.
Fig. 5 is a mapping spectrum of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in example 1.
FIG. 6 is a linear voltammogram of an oxygen evolution reaction of the electrocatalyst materials prepared in examples 1-3, comparative examples 1-4 in an oxygen saturated 1mol/L KOH solution.
FIG. 7 is a graph of the stability of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in example 1 in an oxygen-saturated 1mol/L KOH solution.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
The 304 stainless steel used in the examples was purchased from Wuxin Maihui, Inc. and had a thickness of 0.1mm, and its Scanning Electron Microscope (SEM) image is shown in FIG. 1.
The sodium hydrogen selenide solution used in the embodiment is obtained by adopting the following preparation method: in N2Adding selenium powder into NaBH under atmosphere4Stirring at room temperature until selenium powder is completely dissolved in the deionized water to obtain a sodium hydroselenide solution, wherein the selenium powder and NaBH4The mass ratio of the sodium hydrogen selenide solution to the sodium hydrogen selenide solution is 1:1, and the concentration of the obtained sodium hydrogen selenide solution is 30 mmol/L.
Example 1
A preparation method of a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
(1) cutting selected 304 stainless steel into 1 × 3cm2Sequentially using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water to respectively ultrasonically clean the cut stainless steel for 30min, and after cleaning, putting the stainless steel into a vacuum drying oven to be dried for 24h at 60 ℃ in vacuum to obtain pretreated stainless steel; then, putting 40mL of prepared 6mol/L potassium hydroxide solution and the pretreated stainless steel into a high-pressure closed reaction kettle, and carrying out hydrothermal reaction for 16h at 160 ℃ in an oven; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain a nickel ferrite spinel/nickel oxyhydroxide precursor;
(2) putting the nickel hercynite/nickel oxyhydroxide precursor obtained in the step (1) and 30mL of 30mmol/L sodium hydroselenide solution into a high-pressure closed reaction kettle, and then carrying out hydrothermal selenization for 24 hours in an oven at 180 ℃; washing the obtained product with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
The application of the electrocatalyst material in the electrolysis of water and oxygen evolution of alkaline aqueous solution comprises the following steps:
(1) preparation of electrolytic solutions
Weighing 56.1g of potassium hydroxide, dissolving the potassium hydroxide in a beaker filled with 400mL of distilled water, stirring and dissolving the potassium hydroxide for 10min under magnetic stirring to form a uniform and transparent solution, then pouring the solution into a 1000mL volumetric flask, fixing the volume to the scale mark of the volumetric flask to form a 1mol/L potassium hydroxide solution, taking the uniform 100mL potassium hydroxide solution, introducing oxygen for half an hour to remove other dissolved gases in the solution to form an oxygen-saturated potassium hydroxide solution.
(2) Electrochemical testing of electrolyzed water
Establishing a three-electrode system in an electrolytic cell, performing an electrochemical water decomposition test by using the oxygen-saturated potassium hydroxide solution as an electrolyte solution, the synthesized selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material as a working electrode, a double-salt bridge silver/silver chloride electrode as a reference electrode and a platinum sheet as a counter electrode, performing a linear scanning voltammetry curve test in a voltage range of 1.2-1.8V (V vs RHE) to detect the catalytic performance of the catalyst by using a used electrochemical workstation of Shanghai Chenghua 660E; in addition, the three-electrode system is adopted to synthesize the electrocatalyst material with the current density of 10mA/cm2And 100mA/cm2A chronoamperometric test (i-t) was performed at the corresponding voltage to check the stability of the material.
The X-ray diffraction (XRD) spectrum of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example is shown in FIG. 2, and the analyzed composition is NiFe2O4(ii) a The Raman spectrum of the selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example is shown in fig. 3, and the composition is NiOOH by analysis, the mapping spectrum of the selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example is shown in fig. 5, and the composition of its nanoparticles is NiFe by analysis2OxSe4-xWherein x is in the range: x is more than 0 and less than 4, and the composition of the nano-sheet is NiOOH. In conclusion, the prepared selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material has the composition of NiFe2OxSe4-xAnd NiOOH.
A Scanning Electron Microscope (SEM) image of the selenium-doped ferronickel spinel/nickel oxyhydroxide composite electrocatalyst material prepared in this embodiment is shown in fig. 4, and as can be seen from fig. 4, the obtained product has a microscopic morphology in which selenium-doped ferronickel spinel nanoparticles and nickel oxyhydroxide nanosheets are interconnected, the diameter of the selenium-doped ferronickel spinel nanoparticles is 200-400 nm, the thickness of the nickel oxyhydroxide nanosheets is 8-15 nm, and the transverse length is 1-3 μm. The formation of the three-dimensional heterostructure can improve the mass transfer capacity of the catalyst, is beneficial to the exposure of electrochemical active sites, increases the electrochemical active area of materials, and increases the hydrophilicity between the surface of the electrocatalyst and electrolyte, so that the electrocatalyst can be better adsorbed with water molecules, gas can be more quickly removed, and the catalytic activity of the catalyst is improved.
The linear voltammogram of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example in an oxygen-saturated 1mol/L KOH solution is shown in FIG. 6, and it can be seen from FIG. 6 that 10mA/cm is reached2The overpotential required for the current density is only 182mV, and the overpotential of the synthetic material is very low for industrial electrocatalytic water decomposition reactions.
The stability curve of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example in oxygen-saturated 1mol/L KOH solution is shown in FIG. 7, and it can be seen from FIG. 7 that at the corresponding 10mA/cm2The catalytic activity can be maintained at 500h at a corresponding voltage of 100mA/cm2The catalytic activity can be maintained at 300h under the applied voltage, and the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material synthesized by the invention has extremely excellent stability.
Example 2
A preparation method of a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
(1) cutting selected 304 stainless steel into 1 × 3cm2Sequentially using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water to respectively ultrasonically clean the cut stainless steel for 30min, and after cleaning, putting the stainless steel into a vacuum drying oven to be dried for 24h at 60 ℃ in vacuum to obtain pretreated stainless steel; then, putting 40mL of prepared 6mol/L potassium hydroxide solution and the pretreated stainless steel into a high-pressure closed reaction kettle, and carrying out hydrothermal reaction for 16h at 160 ℃ in an oven; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain a nickel ferrite spinel/nickel oxyhydroxide precursor;
(2) putting the nickel hercynite/nickel oxyhydroxide precursor obtained in the step (1) and 30mL of 30mmol/L sodium hydroselenide solution into a high-pressure closed reaction kettle, and then carrying out hydrothermal selenization for 16h in an oven at the temperature of 180 ℃; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
The procedure of applying the above electrocatalyst material to an aqueous alkaline solution to electrolyze water to evolve oxygen is as described in example 1.
The linear voltammogram of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example in an oxygen-saturated 1mol/L KOH solution is shown in FIG. 6, and it can be seen from FIG. 6 that 10mA/cm is reached2The overpotential required for the current density is only 226mV, and the overpotential of the synthetic material is very low for industrial electrocatalytic water decomposition reactions.
Example 3
A preparation method of a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
(1) cutting selected 304 stainless steel into 1 × 3cm2Sequentially using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water to respectively ultrasonically clean the cut stainless steel for 30min, and after cleaning, putting the stainless steel into a vacuum drying oven to be dried for 24h at 60 ℃ in vacuum to obtain pretreated stainless steel; then 40mL of the prepared 6mol/L potassium hydroxide solution was mixed withPutting the treated stainless steel into a high-pressure closed reaction kettle, and performing hydrothermal reaction for 16 hours in an oven at 160 ℃; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain a nickel ferrite spinel/nickel oxyhydroxide precursor;
(2) placing the nickel hercynite/nickel oxyhydroxide precursor obtained in the step (1) and 30mL of 30mmol/L sodium hydroselenide solution into a high-pressure closed reaction kettle, and then carrying out hydrothermal selenization for 32h in an oven at the temperature of 180 ℃; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
The procedure of applying the above electrocatalyst material to an aqueous alkaline solution to electrolyze water to evolve oxygen is as described in example 1.
The linear voltammogram of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared in this example in an oxygen-saturated 1mol/L KOH solution is shown in FIG. 6, and it can be seen from FIG. 6 that 10mA/cm is reached2The overpotential required for the current density is only 232mV, and the overpotential of the synthetic material is very low enough to be used in the industrial electrocatalytic water decomposition reaction.
Comparative example 1
Mixing 5mg of RuO2The powder was dispersed in 1mL of a mixed solvent of water/anhydrous ethanol at a volume ratio of 1:1 together with 50. mu.L of Nafion solution (. about.5%, Sigma-Aldrich), and sonicated for 30 minutes. Then, 5 μ L of the above solution was dropped on the surface of a Glassy Carbon (GC) electrode and naturally dried to obtain an electrocatalyst material.
The procedure of applying the above electrocatalyst material to an aqueous alkaline solution to electrolyze water to evolve oxygen is as described in example 1.
The linear voltammogram of the electrocatalyst material prepared in this comparative example in a 1mol/L KOH solution saturated with oxygen is shown in FIG. 6, and it can be seen from FIG. 6 that 10mA/cm was reached2The overpotential required by the current density is 306mV, and the performance is inferior to the selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material prepared by the invention.
Comparative example 2
A method for preparing a nickel herelene/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
(1) cutting selected 304 stainless steel into 1 × 3cm2Sequentially using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water to respectively ultrasonically clean the cut stainless steel for 30min, and after cleaning, putting the stainless steel into a vacuum drying oven to be dried for 24h at 60 ℃ in vacuum to obtain pretreated stainless steel; then, putting 40mL of prepared 6mol/L potassium hydroxide solution and the pretreated stainless steel into a high-pressure closed reaction kettle, and carrying out hydrothermal reaction for 16h at 160 ℃ in an oven; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain a nickel ferrite spinel/nickel oxyhydroxide precursor;
(2) and (2) performing high-temperature gas phase selenization on the nickel hercynite/nickel oxyhydroxide precursor obtained in the step (1) in a tube furnace, putting 400mg of selenium powder into an upstream porcelain boat, putting the precursor at the downstream, heating the precursor to 400 ℃ at the temperature rise rate of 5 ℃/min, keeping the temperature for 120min, naturally cooling a sample along with the furnace, washing the sample by deionized water and absolute ethyl alcohol, and drying the sample for 24h at 90 ℃ in a vacuum drying oven to obtain the nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
The procedure of applying the above electrocatalyst material to an aqueous alkaline solution to electrolyze water to evolve oxygen is as described in example 1.
The linear voltammogram of the electrocatalyst material prepared in this comparative example in 1mol/L KOH solution saturated with oxygen is shown in FIG. 6, reaching 10mA/cm2The overpotential required by the current density is 281mV, and the performance is inferior to the selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material prepared by the invention.
Comparative example 3
A preparation method of a selenized stainless steel electrocatalyst material comprises the following steps:
(1) cutting selected 304 stainless steel into 1 × 3cm2Respectively ultrasonically cleaning the cut stainless steel for 30min by using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water in sequence, and then putting the stainless steel into a vacuum drying oven at 60 ℃ to be vacuum cleanedAir-drying for 24 hours to obtain pretreated stainless steel;
(2) placing the pretreated stainless steel obtained in the step (1) and 30mL of 30mmol/L sodium hydroselenide solution in a high-pressure closed reaction kettle, and then performing hydrothermal selenization for 24 hours in an oven at 180 ℃; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
The procedure of applying the above electrocatalyst material to an aqueous alkaline solution to electrolyze water to evolve oxygen is as described in example 1.
The linear voltammetry curve of the selenized stainless steel electrocatalyst material prepared in the comparative example in 1mol/L KOH solution saturated with oxygen is shown in FIG. 6, and reaches 10mA/cm2The overpotential required by the current density is 323mV, and the performance is inferior to the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared by the invention.
Comparative example 4
A preparation method of a nickel hercynite/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
cutting the selected 304 stainless steel substrate material into 1 x 3cm2Sequentially using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water to respectively ultrasonically clean the cut stainless steel substrate for 30min, and after cleaning, putting the stainless steel substrate into a vacuum drying oven to be dried for 24h under the temperature of 60 ℃ to obtain the pretreated stainless steel substrate; then, putting 40mL of prepared 6mol/L potassium hydroxide solution and the pretreated stainless steel substrate into a high-pressure closed reaction kettle, and carrying out hydrothermal reaction for 16h at 160 ℃ in an oven; washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 90 ℃ for 24h to obtain the nickel hercynite/nickel oxyhydroxide composite electrocatalyst material.
The procedure of applying the above electrocatalyst material to an aqueous alkaline solution to electrolyze water to evolve oxygen is as described in example 1.
The linear voltammetry curve of the nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared by the comparative example in a 1mol/L KOH solution is shown in FIG. 6 and reaches mA/cm2Excess required for current densityThe potential is 259mV, and the performance is superior to the prior noble metal-based catalyst RuO2The performance of the composite electrocatalyst material is inferior to that of the selenium-doped nickel ferrite/nickel oxyhydroxide composite electrocatalyst material prepared by the invention.
The experiments prove that the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material prepared by the invention has higher catalytic activity and stability.
Claims (9)
1. The selenium-doped ferronickel spinel/nickel oxyhydroxide composite electrocatalyst material is characterized in that the microstructure of the composite electrocatalyst material is that selenium-doped ferronickel spinel nano-particles and nickel oxyhydroxide nano-sheets are mutually connected, the diameter of the selenium-doped ferronickel spinel nano-particles is 200-400 nm, the thickness of the nickel oxyhydroxide nano-sheets is 8-15 nm, and the transverse length of the nickel oxyhydroxide nano-sheets is 1-3 mu m;
the preparation method of the selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material comprises the following steps:
(1) carrying out hydrothermal reaction on the pretreated stainless steel and an alkaline solution at the temperature of 60-220 ℃ for 6-90 h, and washing and drying after the reaction is finished to obtain a nickel-iron spinel/nickel oxyhydroxide precursor; the concentration of the alkaline solution is 1-20 mol/L; the ratio of the volume of the alkaline solution to the area of the stainless steel is 4-30: 1mL/cm2；
(2) Carrying out hydrothermal accurate selenization on the nickel hercynite/nickel oxyhydroxide precursor obtained in the step (1) and a selenium source solution, and after the reaction is finished, washing and drying to obtain a selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material; the concentration of selenium in the selenium source solution is 2-200 mmol/L; the ratio of the volume of the selenium source solution to the area of the stainless steel is 3-30: 1mL/cm2(ii) a The temperature of the hydrothermal accurate selenization is 20-240 ℃; the hydrothermal accurate selenization time is 0.5-120 h.
2. The selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the stainless steel in step (1) is one of 200 series, 300 series, 400 series, 500 series, 600 series; the thickness of the stainless steel is 0.01-5 mm.
3. The selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the alkaline solution in step (1) is potassium hydroxide solution.
4. The selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the selenium source solution in step (2) is one of a sodium hydroselenide solution, a selenium powder-hydrazine hydrate solution, and a selenium powder-sodium borohydride solution.
5. The selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the pretreatment in step (1) is: and respectively ultrasonically cleaning the stainless steel for 30min by using acetone, ethanol, 2mol/L hydrochloric acid solution and deionized water in sequence, and then drying the stainless steel for 0.5 to 120 hours in vacuum at the temperature of between 25 and 150 ℃.
6. The selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the washing in step (1) is washing with deionized water, absolute ethanol in sequence; the drying is carried out for 0.5-120 h under vacuum at the temperature of 25-150 ℃.
7. The selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the washing in step (2) is washing with deionized water, absolute ethanol in sequence; the drying is carried out for 0.5-120 h under vacuum at the temperature of 25-150 ℃.
8. The selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1, wherein the temperature for hydrothermal precision selenization in step (2) is 120-220 ℃; the hydrothermal accurate selenizing time is 12-48 h; the drying is carried out under vacuum at 90 ℃ for 24 h.
9. The use of the selenium-doped hercynite/nickel oxyhydroxide composite electrocatalyst material according to claim 1 as an anode electrocatalyst for the electrolysis of aqueous alkaline solutions for oxygen evolution.
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