CN117305892A - Preparation method and application of foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst - Google Patents
Preparation method and application of foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst Download PDFInfo
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- CN117305892A CN117305892A CN202311232189.2A CN202311232189A CN117305892A CN 117305892 A CN117305892 A CN 117305892A CN 202311232189 A CN202311232189 A CN 202311232189A CN 117305892 A CN117305892 A CN 117305892A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000006260 foam Substances 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 51
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- UWQFUYSXGDMTGJ-UHFFFAOYSA-N [P].[Fe].[W] Chemical compound [P].[Fe].[W] UWQFUYSXGDMTGJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000013460 polyoxometalate Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
Landscapes
- 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 belongs to the technical field of electrocatalytic material preparation, and in particular relates to a preparation method of a foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst, which comprises the following steps: 1) To be short of the polyoxometalate K 12 H 2 P 2 W 12 O 48 ·24H 2 Mixing O, ferric trichloride, a surfactant and sodium sulfide to prepare an aqueous solution; 2) And (3) adding the foam nickel into the aqueous solution prepared in the step (S1), and preparing the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst by a one-step hydrothermal method. According to the invention, the absent polyacid, the ferric salt and the foam nickel are synergistic, so that the Fe-W-P three-element doped catalyst is prepared, the controllable doping of the nickel sulfide catalyst is realized, the OER catalytic activity of the catalyst is high, the stability is good, and the catalyst has higher practical application value in the electrocatalytic oxygen evolution reaction.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic material preparation, and particularly relates to a preparation method and application of a foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst.
Background
In recent years, the problems of environment and energy are hot spots in the scientific research field, and various novel electrochemical catalysts are promoted to be new, so that the electrochemistry is highly colorful in the energy and environment fields. Among them, hydrogen energy is attracting attention as a sustainable, storable clean energy source. The clean energy which is inconvenient to store, such as wind energy, solar energy, tidal energy and the like is used for supplying power, hydrogen is produced by electrolysis of water, the hydrogen is produced by combustion or a fuel cell, and the product is pure water, so that a green and environment-friendly clean energy system is formed. However, the problems of high cost and high energy consumption exist in the hydrogen production by water electrolysis, especially the high overpotential of the oxygen evolution reaction (ORE) of the anode affects the electrolysis efficiency, while the iridium-based catalyst and the ruthenium-based catalyst have higher OER activity, but have higher cost and are not suitable for large-scale industrial production. Therefore, it is required to develop a catalyst which is low in design cost, excellent in OER catalytic performance and stable.
The foam nickel-supported transition metal catalyst has good application prospect in the field of hydrogen production by water electrolysis, and among a plurality of transition metal-based catalysts, nickel sulfide has low cost, high conductivity and good OER catalytic activity. However, the OER activity of nickel sulfide is to be improved compared to noble metal based catalysts, and doping modification strategies may be employed to improve the OER activity of nickel sulfide. For example, chen et al synthesized copper doped nickel sulfide (Cu-Ni) on foam nickel by a two-step hydrothermal process 3 S 2 /NF) which, when used as an anode material for electrolysis of water, reaches 50mA cm at an overpotential of 270mV -2 The method comprises the steps of carrying out a first treatment on the surface of the Lan et al, one-step solvothermal method for preparing molybdenum-doped nickel sulfide electrocatalyst (Mo-Ni 3 S 2 /NF) only an overpotential of 291mV was required in OER to provide a 100mA cm -2 Is a current density of (a); li et al, one-step preparation of an iron-doped nickel sulfide electrode from NiFe form, which exhibits good OER activity at a current density of 100 mAcm -2 The time overpotential was 290mV. Therefore, the effective doping of high-activity elements becomes an important way for enhancing the catalytic activity of nickel sulfide, but the multi-element catalyst doped with nickel sulfide simultaneously and the preparation of the catalyst at presentThe preparation method is rarely reported.
Disclosure of Invention
The invention aims to provide a preparation method of a foam nickel-loaded Fe-W-P doped nickel sulfide catalyst, so as to obtain the Fe-W-P three-element co-doped nickel sulfide catalyst with high OER catalytic activity and strong stability, thereby being applied to an electrocatalytic oxygen evolution reaction.
In order to achieve the above purpose, the invention provides a preparation method of a foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst, which comprises the following steps:
s1, preparing a hypo-polyoxometalate K 12 H 2 P 2 W 12 O 48 ·24H 2 Mixing O, ferric trichloride, a surfactant and sodium sulfide to prepare an aqueous solution;
s2, adding the foam nickel into the aqueous solution prepared in the step S1, and preparing the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst by a one-step hydrothermal method.
Optionally, in step S1, the short-site polyoxometalate K 12 H 2 P 2 W 12 O 48 ·24H 2 The concentration of O is 1.5-3.0 mmol/L, the concentration of ferric trichloride is 30-50 mmol/L, the concentration of surfactant is 2-3 g/L, and the concentration of sodium sulfide is 60-120 mmol/L.
Optionally, in step S2, adding the foam nickel and the aqueous solution into a reaction kettle, sealing the reaction kettle, then placing the reaction kettle into a hydrothermal box, reacting at a constant temperature of 150 ℃ for more than 5 hours, cooling to room temperature after the reaction is finished, taking out the reacted foam nickel, washing the foam nickel with water and ethanol for several times in sequence, and then drying the foam nickel loaded iron-tungsten-phosphorus doped nickel sulfide catalyst at 60 ℃.
Optionally, in step S2, the nickel foam is pre-treated before being added to the aqueous solution prepared in step S1: the nickel foam is put into 3M hydrochloric acid solution for ultrasonic treatment for 10min, and then the nickel foam is transferred into pure water for ultrasonic treatment for 10min. In the scheme, the nickel oxide layer on the surface of the foam nickel is removed through pretreatment, and pollutants such as grease and the like.
Optionally, in step S2, the nickel foam is cut to a specification of 1cm×4 cm. The foam nickel in this scheme can be placed upright in the reaction kettle.
Optionally, in step S1, the surfactant is one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide and sodium dodecyl sulfate.
The invention also provides the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst prepared by the preparation method, and the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst has high OER catalytic activity and high stability and can be applied to electrocatalytic oxygen evolution reaction.
The scheme has the remarkable advantages and beneficial effects that: in the scheme, the site-deficient polyacid, the ferric salt and the foam nickel have synergistic effect, so that the catalyst doped with tungsten-phosphorus ternary element simultaneously is prepared, the controllable doping of the nickel sulfide catalyst is realized, and the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst in the scheme has high OER catalytic activity and good stability and is 100mA/cm 2 The OER overpotential under the current density is 231mV, so that the method has higher practical application value in the electrocatalytic oxygen evolution reaction. In addition, the preparation method of the scheme has the advantages of simple process, mild condition, low cost and good industrial application value. The scheme utilizes the characteristic that the absent polyacid { P2W12} has strong interaction with iron ions, thus being beneficial to the simultaneous incorporation of several elements into the nickel sulfide structure.
Drawings
FIG. 1 is a scanning electron microscope image of a foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst according to example 1 of the present invention;
FIG. 2 is an EDS spectrum of a foam nickel supported iron-tungsten-phosphorus doped nickel sulfide catalyst of example 1 of the present invention;
FIG. 3 is a graph of current versus time for 25 hours electrolysis of a foam nickel supported iron tungsten phosphorus doped nickel sulfide catalyst according to example 1 of the present invention;
FIG. 4 is a graph comparing the linear sweep voltammograms of the foam nickel supported iron tungsten phosphorus doped nickel sulfide catalysts of example 1 and comparative example 1 of the present invention.
Detailed Description
The following is a further detailed description of the embodiments:
example 1
The embodiment provides a foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst, and the preparation method of the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst comprises the following steps:
step one, preparing an aqueous solution
0.315g of the hypo-polyoxometalate K is weighed respectively 12 H 2 P 2 W 12 O 48 ·24H 2 O (abbreviated as { P2W12 }), 0.540g FeCl 3 、0.39g Na 2 S, 0.145g polyvinylpyrrolidone (PVP), pour the weighed reagent into a beaker and add 50mL deionized water to dissolve, stir at room temperature for 1min.
The preparation method of { P2W12} is as follows:
into a round bottom flask was added 10g Na 2 WO 4 ·2H 2 O and 35mL of water, after dissolution, heated to boiling, 15mL of 85% H was slowly added dropwise 3 PO 4 And 1mL of H was added with stirring 2 O 2 The solution was refluxed for 3h, cooled and then 10g of KCI solid was added and stirred for 1h to give a pale yellow precipitate which was suction filtered. Adding a small amount of water, recrystallizing, filtering, cooling in ice water, and suction filtering. Purifying again, dissolving with small amount of 40deg.C hot water (pH is adjusted to 2 with hydrochloric acid), cooling, and evaporating to obtain yellow crystal K at room temperature 6 [P 2 W 18 O 62 ]·14H 2 And collecting crystals and drying.
83g K are taken in a beaker 6 [P 2 W 18 O 62 ]·14H 2 A sample of O was dissolved in 300mL of water, 48.4g of tris was dissolved in 200mL of water and the 300mL of the aqueous solution was added to obtain a mixed solution. The mixed solution was allowed to stand at room temperature for 0.5h, followed by addition of 80g of potassium chloride. After complete dissolution, 55.3g of potassium carbonate is added into 200mL of water, and the 200mL of potassium carbonate aqueous solution is added into the mixed solution, and is stirred vigorously for 15min, filtered on a white precipitation sand core funnel which appears after several minutes, suction filtered for 12h, washed with 50mL of ethanol for 2-3 min, and finally air-dried for 3 days to obtain K 12 H 2 P 2 W 12 O 48 ·24H 2 O。
Step two, preparing a foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst
1) Pretreatment of foam nickel: the nickel foam was cut into a rectangle of 1cm x 4cm and placed in a beaker containing 3M hydrochloric acid solution for 10min of ultrasonic treatment, and then the nickel foam was transferred to a beaker containing pure water for 10min of ultrasonic treatment.
2) Hydrothermal reaction: and (3) placing the two pretreated foam nickel pieces into a reaction kettle, pouring the aqueous solution prepared in the first step into the reaction kettle in time, then sealing the reaction kettle, and placing the reaction kettle into an oven for reaction for 6 hours at the constant temperature of 150 ℃. After the reaction is finished, cooling to room temperature, and taking out the foam nickel after the reaction.
3) Cleaning and drying: washing the reacted foam nickel by using deionized water and absolute ethyl alcohol in sequence, washing for three times respectively, and washing impurities on the reacted foam nickel. Then drying in a vacuum drying oven at 60 ℃ to obtain the foam nickel-loaded Fe-W-P doped nickel sulfide catalyst, which is called Fe { P2W12} -Ni for short 3 S 2 @NF。
The scanning result of the electron microscope of the foam nickel-loaded Fe-W-P doped nickel sulfide catalyst in the embodiment is shown in figure 1, and the graph shows that the catalyst grows a uniformly dispersed nano structure on the surface of the foam nickel. The EDS energy spectrum is shown in figure 2, and the catalyst contains Fe, W, ni, P, S elements, which shows that the embodiment successfully prepares the catalyst doped with three elements of Fe, W and P simultaneously; as can be seen from FIG. 3, the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst in the embodiment has stable current density in the 25h electrolysis process, and the current fluctuation range is between 55.49mA and 50.84mA, and the fluctuation interval is small, thus proving that the stability is high. In addition, the nickel sulfide catalyst doped with Fe, W and P was sandwiched by platinum electrode clamps as a working electrode, pt plate as a counter electrode, hg/HgO as a reference electrode, 1M KOH as an electrolyte, and was connected by an electrochemical workstation and then scanned by linear voltammetry, as shown in FIG. 4, at 100mA/cm 2 Fe { P2W12} -Ni at current density of (C) 3 S 2 The OER overpotential of the @ NF catalyst was 231mV.
Example 2
This embodiment differs from embodiment 1 in that: the { P2W12} amount weighed in step one of this example was different from the { P2W12} amount weighed in step one of example 1, and the rest was the same, specifically, the { P2W12} amount weighed in step one of this example was 0.285g.
The foam nickel-supported Fe-W-P doped nickel sulfide catalyst in this example was clamped by a platinum electrode clamp as the working electrode, a Pt plate as the counter electrode, hg/HgO as the reference electrode, 1M KOH as the electrolyte, and was subjected to linear voltammetry scanning at 100mA/cm after connection by an electrochemical workstation 2 The OER overpotential at the current density of (c) was 248mV.
Example 3
This embodiment differs from embodiment 1 in that: the { P2W12} amount weighed in step one of this example was different from the { P2W12} amount weighed in step one of example 1, and the rest was the same, specifically, the { P2W12} amount weighed in step one of this example was 0.570g.
The foam nickel-supported Fe-W-P doped nickel sulfide catalyst in this example was clamped by a platinum electrode clamp as the working electrode, a Pt plate as the counter electrode, hg/HgO as the reference electrode, 1M KOH as the electrolyte, and was subjected to linear voltammetry scanning at 100mA/cm after connection by an electrochemical workstation 2 The OER overpotential at the current density of (c) was 237mV.
Comparative example 1
This embodiment differs from embodiment 1 in that: step one of this comparative example is different from step one of example 1, and the rest is the same, specifically, step one of this comparative example is as follows:
0.315g of reagent H was weighed separately 3 O 40 PW 12 ·xH 2 O{PW12}、0.540g FeCl 3 、0.39g Na 2 S, 0.145g polyvinylpyrrolidone (PVP), pour the weighed reagent into a beaker and add 50mL deionized water to dissolve, stir at room temperature for 1min. Wherein, { PW12} is a purchased commercial product, specifically a phosphotungstic acid hydrate product produced by Michelin corporation.
Foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst in comparative exampleAbbreviated as Fe { PW12} -Ni 3 S 2 @nf. In this comparative example, the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst of this comparative example was sandwiched by platinum electrode clamps as a working electrode, pt sheet as a counter electrode, hg/HgO as a reference electrode, an electrolyte solution of 1M KOH, and was connected by an electrochemical workstation and then scanned by linear voltammetry, as shown in fig. 4, at 100mA/cm 2 The OER overpotential at the current density of (c) was 269mV.
The foregoing is merely an embodiment of the present invention, the present invention is not limited to the field of this embodiment, and the specific structures and features well known in the schemes are not described in any way herein, so that those skilled in the art will know all the prior art in the field before the application date or priority date, and will have the capability of applying the conventional experimental means before the date, and those skilled in the art may, in light of the teaching of this application, complete and implement this scheme in combination with their own capabilities, and some typical known structures or known methods should not be an obstacle for those skilled in the art to practice this application. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the structure of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the present invention. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (8)
1. A preparation method of a foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst is characterized by comprising the following steps of: the method comprises the following steps:
s1, preparing a hypo-polyoxometalate K 12 H 2 P 2 W 12 O 48 ·24H 2 Mixing O, ferric trichloride, a surfactant and sodium sulfide to prepare an aqueous solution;
s2, adding the foam nickel into the aqueous solution prepared in the step S1, and preparing the foam nickel-loaded iron-tungsten-phosphorus doped nickel sulfide catalyst by a one-step hydrothermal method.
2. The method for preparing the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst according to claim 1, which is characterized by comprising the following steps: in step S1, the short-site polyoxometalate K 12 H 2 P 2 W 12 O 48 ·24H 2 The concentration of O is 1.5-3.0 mmol/L, the concentration of ferric trichloride is 30-50 mmol/L, the concentration of surfactant is 2-3 g/L, and the concentration of sodium sulfide is 60-120 mmol/L.
3. The method for preparing the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst according to claim 1, which is characterized by comprising the following steps: in the step S2, adding foam nickel and aqueous solution into a reaction kettle, sealing the reaction kettle, then placing the reaction kettle into a hydrothermal box, reacting for more than 5 hours at a constant temperature of 150 ℃, cooling to room temperature after the reaction is finished, taking out the foam nickel after the reaction, washing the foam nickel with water and ethanol for a plurality of times in sequence, and then drying the foam nickel loaded iron-tungsten-phosphorus doped nickel sulfide catalyst at a temperature of 60 ℃.
4. The method for preparing the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst according to claim 1, which is characterized by comprising the following steps: in step S2, the nickel foam is pretreated before being added into the aqueous solution prepared in step S1: the nickel foam is put into 3M hydrochloric acid solution for ultrasonic treatment for 10min, and then the nickel foam is transferred into pure water for ultrasonic treatment for 10min.
5. The method for preparing the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst according to claim 1, which is characterized by comprising the following steps: in step S2, the nickel foam is cut to a specification of 1cm by 4 cm.
6. The method for preparing the foam nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst according to claim 1, which is characterized by comprising the following steps: in step S1, the surfactant is one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide and sodium dodecyl sulfate.
7. The foamed nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst prepared by the preparation method of any one of claims 1-6.
8. Use of the foamed nickel-supported iron-tungsten-phosphorus doped nickel sulfide catalyst prepared by the preparation method according to any one of claims 1-6 in electrocatalytic oxygen evolution reaction.
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