CN114622243A - Fe-doped Ni3S2Preparation method and application of electrode material - Google Patents
Fe-doped Ni3S2Preparation method and application of electrode material Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 129
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 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 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012153 distilled water Substances 0.000 claims abstract description 17
- 239000006260 foam Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000004809 Teflon Substances 0.000 claims abstract description 8
- 229920006362 Teflon® Polymers 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000010287 polarization Effects 0.000 description 7
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010301 surface-oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
- 230000000877 morphologic effect Effects 0.000 description 1
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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Abstract
The invention belongs to the technical field of electrode material preparation, and relates to Fe-doped Ni3S2The preparation method of the electrode material comprises the following steps; foam nickel pretreatment: placing the foamed nickel in dilute hydrochloric acid, performing ultrasonic treatment to remove a surface oxide layer, performing ultrasonic treatment in distilled water and absolute ethyl alcohol in sequence, and drying for later use; fe doped Ni3S2Preparing an electrode material: respectively placing thiourea, ferric nitrate and distilled water in a Teflon liner, stirring for 30 minutes to form a mixed solution, immersing foamed nickel in the mixed solution, carrying out hydrothermal reaction, controlling the temperature at 120 ℃, keeping the temperature for 12 hours, and cooling after the reaction is finished, wherein the electrode material is loaded on the nickel-loaded electrode materialThe foam nickel is cleaned and dried to obtain the unique Fe-doped Ni3S2An electrode material. The Fe of the invention is doped with Ni3S2The high specific surface area of the electrode material can fully expose the catalytic reaction active sites on the surface of the electrode material, and meanwhile, the activity of the catalytic active sites can be improved through the adjustment of the electronic structure of the material induced by Fe doping.
Description
Technical Field
The invention relates to Fe-doped Ni3S2A preparation method of the electrode material. Belongs to the technical field of electrode material preparation.
Background
In recent years, the serious dependence on traditional fossil energy has led to an increasing number of energy and environmental problems. In the face of the above serious crisis, one of the important measures is to develop clean renewable energy sources, such as solar energy, hydroelectric energy, wind power energy, geothermal energy, hydrogen energy, and the like. The hydrogen energy has the advantages of wide preparation mode, high energy density, water serving as a product after energy release and the like, and becomes one of ideal energy carriers for solving the current energy and environmental crisis.
At present, the hydrogen production mode mainly comprises the modes of hydrogen production by fossil energy, hydrogen purification by industrial byproducts, hydrogen production by photocatalysis, hydrogen production by electrocatalysis water decomposition and the like. The hydrogen production mode of fossil energy and industrial byproducts has the problem of environmental pollution, and the cost of photocatalytic hydrogen production is high. Compared with the above hydrogen production mode, the hydrogen production by electrolyzing water by using secondary energy can avoid the defects mentioned above, and can become an ideal way for industrially obtaining a large amount of hydrogen in the future. Cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER) are two basic reactions of water decomposition. HER involves a two electron transfer process and OER involves a complex four electron transfer process, resulting in slow kinetics of OER. This will greatly increase the energy consumption for water splitting, which becomes a bottleneck limiting the efficiency of water electrolysis. Therefore, the development of cheap and efficient OER electro-catalyst is one of the core basic scientific problems for developing the water electrolysis hydrogen production technology.
Currently noble metal oxide RuO2、IrO2Are considered to be the most efficient OER electrocatalysts. But the price is high, the resource is rare, and the wide application in large-scale industrial production is difficult. Therefore, the development of cheap and efficient OER electro-catalyst is an urgent need to promote the development of water electrolysis hydrogen production technology. In recent years, thanks to low price, metallic conductivity, flexible electronic structure and intrinsic catalytic activity, the nickel sulfide (Ni) of the type of the ore of the Hizisha sulfide3S2) The water decomposition electrocatalyst is obtained by the wide attention in the technical field. But now Ni3S2Show that the OER catalytic activity needs to be further improved. The increase of the number of catalytic active sites on the surface of the electrode material and the improvement of the activity of a single site are two important entry points for improving the catalytic performance of the electrode material.
At present, a microspherical Fe-doped nickel disulfide nano-structure material composed of nano-sheets, a preparation method and an application (CN110227496A) are prepared by dissolving nickel salt, iron salt and thiourea in ethylene glycol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product3S2A nanostructured material. Compared with the prior art, the preparation method provided by the invention has the advantages that nickel salt is not needed, the foam nickel is directly used as a nickel source to carry out hydrothermal reaction, and the preparation cost can be further reduced. Compared with the prior art, the nano-sheet synthesized by the invention has a morphological structure, and the nano-sheet has weak agglomeration behavior, so that the nano-sheet is more beneficial to the exposure of catalytic active sites on the surface of an electrode material. The electrochemical active area increased by the nano-sheet structure and the catalytic site activity improved by Fe doping are utilized. The Fe doped Ni provided by the invention3S2Compared with the patent documents, the nano-structure electrode material used as the oxygen evolution reaction electrocatalyst has the advantages of excellent catalytic performance, simple preparation process and low cost.
Disclosure of Invention
The invention provides Fe-doped Ni3S2Preparation method and application of electrode material, namely Fe-doped Ni is synthesized by simple one-step hydrothermal method3S2And the OER catalytic performance is improved.
In order to achieve the purpose, the technical scheme of the invention is as follows: firstly, placing the cut foam nickel in dilute hydrochloric acid, and carrying out ultrasonic treatment to remove a surface oxide layer. And then carrying out hydrothermal reaction by taking foamed nickel as a nickel source, thiourea as a sulfur source and ferric nitrate as an iron source. The reaction kettle is kept at the temperature of 120 ℃ for 12 hours. Finally preparing Fe-doped Ni3S2An electrode material. The nano-sheet structure remarkably increases the specific surface area of the material and exposes more catalytic active sites. Meanwhile, the introduction of Fe can adjust the electronic structure of the material and improve the activity of catalytic active sites. The two are synergistic to improve the OER catalytic performance of the electrode material.
Fe doped Ni3S2The preparation method of the electrode material comprisesThe method comprises the following steps: step one, foam nickel pretreatment: placing the foamed nickel cut into the specification of 3cm x 1cm into dilute hydrochloric acid, performing ultrasonic treatment for 20 minutes to remove a surface oxidation layer, performing ultrasonic treatment for 20 minutes in sequence in distilled water and absolute ethyl alcohol respectively, and finally performing heat preservation for 8 hours at the temperature of 60 ℃ in a vacuum drying oven, and drying for later use;
step two, doping Fe with Ni3S2Preparing an electrode material: 1.5mmoL of thiourea and a certain amount of ferric nitrate were weighed, added to a Teflon liner having a volume of 20mL, and 15mL of distilled water was measured. And after stirring for 30 minutes, immersing the pretreated foamed nickel into the mixed solution to perform hydrothermal reaction. The reaction kettle is kept at the temperature of 120 ℃ for 12 hours. And after natural cooling, sequentially washing the reacted foam nickel by distilled water and alcohol, and finally, preserving the heat for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain the electrode material.
Preferably, the molar amount of the iron nitrate is 0.15 mmoL.
Preferably, the molar amount of the iron nitrate is 0.45 mmoL.
Preferably, the molar amount of the ferric nitrate is 0.9mmoL, and the obtained electrode material has a sheet structure.
The volume of the Teflon liner is 20mL, and the foamed nickel is cut into the specification of 3cm x 1 cm.
And step two, after the reaction is finished and the nickel foam loaded with the electrode material is cooled, sequentially washing the nickel foam with distilled water and alcohol, and then preserving the heat for 8 hours in a vacuum drying oven at the temperature of 60 ℃.
Fe-doped Ni3S2Fe-doped Ni prepared by preparation method of electrode material3S2An electrode material.
Fe-doped Ni3S2The application of the electrode material in catalytic oxygen evolution in 1M KOH alkaline electrolyte, and the electrode material OER electrocatalytic performance test: and carrying out OER (organic electroluminescent) electrocatalysis performance test on the electrode material by adopting a three-electrode system. The electrolyte is 1M KOH alkaline solution, and a nickel foam, a silver-silver chloride electrode and a graphite rod which are loaded with electrode materials are respectively used as a working electrode, a reference electrode and a counter electrode. The OER catalytic performance is evaluated by a Linear Sweep Voltammetry (LSV) polarization curve.
Compared with the prior art, the invention has the beneficial effects that:
the invention obtains Fe-doped Ni by a hydrothermal method3S2The electrode material has high specific surface area, and can fully expose catalytic reaction active sites on the surface of the electrode material, and meanwhile, the activity of the catalytic active sites can be improved through the adjustment of the electronic structure of the material induced by Fe doping. The electrode material obtained by the invention shows excellent OER electro-catalysis performance in alkaline environment, and 100mA/cm2The overpotential at high current density is only 271 mV. Fe doped Ni obtained by the invention3S2The electrode material is prepared by a one-step hydrothermal method, and the preparation process is simple. The preparation method of the invention does not need nickel salt, directly takes the foam nickel as the nickel source, and has low cost. And the molar weight of the ferric nitrate is 0.9mmoL, so that the sheet electrode material can be generated, and the molar weight of the ferric nitrate is 0.15 and 0.45mmoL, so that the granular electrode material is obtained.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an X-ray diffraction (XRD) pattern of an electrode material obtained in example 1 of the present invention, and a phase characterization is performed;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the electrode material obtained in example 1 of the present invention, and the morphology thereof was characterized;
FIG. 3 is a LSV polarization curve of the electrode material obtained in example 1 of the present invention, characterizing the OER electrocatalytic performance.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
firstly, foam nickel pretreatment: and (3) placing the foamed nickel cut into the specification of 3cm x 1cm into dilute hydrochloric acid, carrying out ultrasonic treatment for 20 minutes to remove a surface oxidation layer, then sequentially carrying out ultrasonic treatment in deionized water and absolute ethyl alcohol for 20 minutes respectively, placing the cleaned foamed nickel into a vacuum drying oven to be dried for 8 hours, and setting the temperature of the drying oven to be 60 ℃ to obtain the pretreated foamed nickel.
Step two Fe doping Ni3S2Preparing an electrode material: 1.5mmoL of thiourea and a certain amount of ferric nitrate were weighed, added to a Teflon liner having a volume of 20mL, and 15mL of distilled water was measured. And after stirring for 30 minutes, immersing the pretreated foamed nickel into the mixed solution to perform hydrothermal reaction. The reaction kettle is kept at the temperature of 120 ℃ for 12 hours. After natural cooling, the foam nickel after reaction is washed by distilled water and alcohol in sequence, and finally is kept at the temperature of 60 ℃ for 8 hours in a vacuum drying oven to obtain Fe-doped Ni3S2An electrode material. It is required to be noted that the shape and structure of the electrode material are different by changing the addition amount of ferric nitrate, and when the addition molar weight is 0.9mmoL, the flaky Fe-doped Ni can be obtained3S2An electrode material.
Comparative example 1:
Ni3S2preparing an electrode material:
firstly, foam nickel pretreatment: and (3) placing the foamed nickel cut into the specification of 3cm x 1cm into dilute hydrochloric acid, performing ultrasonic treatment for 20 minutes to remove a surface oxidation layer, performing ultrasonic treatment in distilled water and absolute ethyl alcohol for 20 minutes respectively in sequence, and finally drying in a vacuum drying oven for 8 hours, wherein the temperature of the drying oven is set to be 60 ℃, so as to obtain the pretreated foamed nickel.
Step II Ni3S2Preparing an electrode material: 1.5mmoL of thiourea was weighed and added to a Teflon liner of 20mL volume, and then 15mL of distilled water was weighed and added to the Teflon liner. And after stirring for 30 minutes, immersing the pretreated foamed nickel into the mixed solution for hydrothermal reaction. The reaction kettle is arrangedThe temperature is kept at 120 ℃ for 12 hours. After natural cooling, the reacted foam nickel is washed by distilled water and alcohol in turn, and finally is kept at the temperature of 60 ℃ for 8 hours in a vacuum drying oven to obtain Ni3S2And (3) an electrode material.
Example 2:
the same as in example 1, except that the molar amount of iron nitrate was 0.15 mmoL.
Example 3:
the same as in example 1, except that the molar amount of iron nitrate was 0.45 mmoL.
Referring to fig. 1: in the second step of preparing the electrode material, Fe is doped with Ni according to the addition amounts of ferric nitrate (0.15, 0.45 and 0.9mmoL)3S2The electrode materials are respectively named as Fe0.15-Ni3S2、Fe0.45-Ni3S2And Fe0.9-Ni3S2. Characteristic peak and Ni of diffraction pattern of all electrode materials3S2The standard XRD spectrum (standard card PDF, No.44-1418) and the Ni standard XRD spectrum (standard card PDF, No.04-0850) correspond. The characteristic peak corresponding to Ni is derived from the elemental base nickel. The obtained electrode materials are all pure phase Ni3S2. Further illustrating the doping of Fe into Ni3S2In the crystal lattice, the electronic structure of the electrode material is affected, and the electrocatalytic activity may be improved.
Referring to FIG. 2, FIGS. 2(a), (b), (c) and (d) are respectively the electrode materials Ni3S2、Fe0.15-Ni3S2、 Fe0.45-Ni3S2And Fe0.9-Ni3S2SEM image of (d). It can be seen that in the second step of preparing the electrode material, the appearance of the reaction product is affected by different addition amounts of the ferric nitrate. As the addition amount of the ferric nitrate is increased, the morphology of the electrode material is changed from granular shape. When the addition amount of ferric nitrate is 0.9mmoL, the Fe-doped Ni is prepared3S2The electrode material is flaky, so that the specific surface area of the material is remarkably increased, more catalytic active sites are exposed, and the electrocatalytic activity is facilitated.
Electrode materialOER electrocatalytic performance test: the OER electrocatalytic performance test adopts a Shanghai Chenghua CHI760E electrochemical workstation, and the test temperature is room temperature. During testing, a standard three-electrode system is selected, foamed nickel loaded with electrode materials is used as a working electrode, a silver-silver chloride electrode is used as a reference electrode, and a graphite rod is used as a counter electrode. The electrolyte used for the electrocatalytic test was a 1M KOH alkaline solution. Before testing the OER catalytic performance, the working electrode is activated by cyclic voltammetry to stabilize the performance. The voltage window was set to a voltage interval of 0-1V, a scan rate of 100mV/S, and a cycle number of 40. After the activation treatment, the OER catalytic performance is evaluated by testing the LSV polarization curve of the working electrode. The voltage window was set to a voltage interval of 0-1V and the scan rate was 5 mV/S. The potential in the obtained LSV polarization curve needs to be first converted into a potential for the reversible hydrogen electrode, and the conversion formula is eree ═ EAg/AgCl+0.197V +0.059 XpH, where ERHERelative to the potential of the reversible hydrogen electrode, EAg/AgClIs the measurement potential. Ohmic compensation of the potential in the LSV polarization curve is also required to account for the voltage drop caused by ohmic polarization during electrocatalysis.
FIG. 3 is a LSV polarization curve of the electrode material prepared in this example. It can be seen that the more the iron nitrate is added in the second preparation step, the stronger the OER catalytic performance of the obtained electrode material is. 100mA/cm2The overpotential of the electrode material at high current density is 477mV (Ni)3S2)、420mV(Fe0.15-Ni3S2)、 337mV(Fe0.45-Ni3S2) And 271mV (Fe)0.9-Ni3S2)。100mA/cm2An overpotential of only 271mV at high current density indicates Fe0.9-Ni3S2The electrode material has excellent OER electrocatalytic performance. Analysis of FIGS. 1-3 taken together, Fe doped Ni3S2The excellent OER catalytic performance of the electrode material is derived from the fact that the number of exposed catalytic active sites is increased due to the appearance, and the activity of the catalytic active sites is improved due to the adjustment of Fe-doped induced electronic structures.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (9)
1. Fe-doped Ni3S2The preparation method of the electrode material is characterized by comprising the following steps: comprises the following steps;
step one, foam nickel pretreatment: placing the foamed nickel in dilute hydrochloric acid, performing ultrasonic treatment for 20 minutes to remove a surface oxide layer, sequentially performing ultrasonic treatment in distilled water and absolute ethyl alcohol for 20 minutes respectively, and drying for later use;
step two, doping Fe with Ni3S2Preparing an electrode material: respectively placing thiourea, ferric nitrate and distilled water in a Teflon liner, stirring for 30 minutes to form a mixed solution, immersing the foamed nickel pretreated in the step one in the mixed solution, carrying out hydrothermal reaction, controlling the temperature at 120 ℃, keeping the temperature for 12 hours, cooling after the reaction is finished, cleaning and drying the foamed nickel loaded with the electrode material to obtain the unique Fe-doped Ni3S2An electrode material.
2. Fe-doped Ni according to claim 13S2The preparation method of the electrode material is characterized by comprising the following steps: the molar weight of the ferric nitrate is 0.15-0.9 mmoL.
3. Fe-doped Ni according to claim 23S2The preparation method of the electrode material is characterized by comprising the following steps: the molar weight of the ferric nitrate is 0.15mmoL, the molar weight of the thiourea is 1.5mmoL, and the volume of the distilled water is 15 mL.
4. Fe-doped Ni according to claim 23S2The preparation method of the electrode material is characterized by comprising the following steps: the molar weight of the ferric nitrate is 0.45mmoL, the molar weight of the thiourea is 1.5mmoL, and the volume of the distilled water is 15 mL.
5. Fe-doped Ni according to claim 23S2The preparation method of the electrode material is characterized by comprising the following steps: the molar weight of the ferric nitrate is 0.9mmoL, the molar weight of the thiourea is 1.5mmoL, and the volume of the distilled water is 15 mL.
6. An Fe doped Ni according to claim 1 or 23S2The preparation method of the electrode material is characterized by comprising the following steps: the volume of the Teflon liner is 20mL, and the foamed nickel is cut into the specification of 3cm x 1 cm.
7. An Fe doped Ni according to claim 1 or 23S2The preparation method of the electrode material is characterized by comprising the following steps: and step two, after the reaction is finished and the nickel foam loaded with the electrode material is cooled, sequentially washing the nickel foam with distilled water and alcohol, and then preserving the heat for 8 hours in a vacuum drying oven at the temperature of 60 ℃.
8. Fe-doped Ni according to any one of claims 1 to 73S2Fe-doped Ni prepared by preparation method of electrode material3S2An electrode material.
9. An Fe doped Ni according to claim 83S2The electrode material is applied to catalytic oxygen evolution in 1M KOH alkaline electrolyte.
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| CN115094472A (en) * | 2022-06-21 | 2022-09-23 | 上海嘉氢源科技有限公司 | Iron-doped Ni 3 S 2 Nano material, preparation method and application |
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