CN111111706A - Nickel selenide sulfide nanorod coated by tungsten-doped nickel selenide sulfide film growing on surface of nickel foam and preparation method and application thereof - Google Patents
Nickel selenide sulfide nanorod coated by tungsten-doped nickel selenide sulfide film growing on surface of nickel foam and preparation method and application thereof Download PDFInfo
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- CN111111706A CN111111706A CN201910669608.6A CN201910669608A CN111111706A CN 111111706 A CN111111706 A CN 111111706A CN 201910669608 A CN201910669608 A CN 201910669608A CN 111111706 A CN111111706 A CN 111111706A
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- selenide sulfide
- tungsten
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 226
- IRLJWYDLXZTYRE-UHFFFAOYSA-N [Se].[S].[Ni] Chemical compound [Se].[S].[Ni] IRLJWYDLXZTYRE-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 113
- 239000002073 nanorod Substances 0.000 title claims abstract description 96
- 239000006260 foam Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 37
- 239000010937 tungsten Substances 0.000 claims abstract description 37
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 36
- 239000011669 selenium Substances 0.000 claims abstract description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 41
- 239000010409 thin film Substances 0.000 claims description 41
- 239000010408 film Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 10
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- FDKWRPBBCBCIGA-REOHCLBHSA-N (2r)-2-azaniumyl-3-$l^{1}-selanylpropanoate Chemical compound [Se]C[C@H](N)C(O)=O FDKWRPBBCBCIGA-REOHCLBHSA-N 0.000 claims description 5
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims description 5
- FDKWRPBBCBCIGA-UWTATZPHSA-N D-Selenocysteine Natural products [Se]C[C@@H](N)C(O)=O FDKWRPBBCBCIGA-UWTATZPHSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- ZKZBPNGNEQAJSX-UHFFFAOYSA-N selenocysteine Natural products [SeH]CC(N)C(O)=O ZKZBPNGNEQAJSX-UHFFFAOYSA-N 0.000 claims description 4
- 229940055619 selenocysteine Drugs 0.000 claims description 4
- 235000016491 selenocysteine Nutrition 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000006258 conductive agent Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 14
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 230000004075 alteration Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000012937 correction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930182853 L-selenocysteine Natural products 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Classifications
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- B01J35/33—
-
- 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
-
- B01J35/396—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
-
- 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
-
- 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
-
- 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
Abstract
The invention provides a nickel selenide sulfide nanorod coated by a tungsten-doped nickel selenide sulfide film growing on the surface of nickel foam, and a preparation method and application thereof, wherein a selenium source is placed in hydrazine hydrate for mechanical stirring and dissolution to obtain a selenium source mixed solution, thiourea, ammonium fluoride and a tungsten source are added into the selenium source mixed solution, and then absolute ethyl alcohol and deionized water are added to finally obtain a mixed solution; pouring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, putting the pretreated nickel foam into the reaction kettle, carrying out hydrothermal treatment, cooling to room temperature of 20-25 ℃, cleaning, drying, and annealing in a protective atmosphere. The preparation method has the advantages of simple preparation process, convenient operation and high repeatability, the nickel selenide sulfide nanorod wrapped by the monatomic tungsten-doped nickel selenide sulfide film grown in situ on the nickel foam is uniformly distributed, has larger length-diameter ratio, can be directly used as an electrode, does not need to additionally add a binder and a conductive agent, and has excellent energy catalysis application prospect.
Description
Technical Field
The invention relates to the technical field of new materials and chemical synthesis, in particular to a nickel selenide sulfide nanorod coated by a tungsten-doped nickel selenide sulfide film growing on the surface of foamed nickel, and a preparation method and application thereof.
Background
With the development of modern society, energy problems and environmental problems become more serious, and therefore, the development and utilization of new energy sources are imminent. The development of high performance fuel cells and metal air cells remains a significant challenge due to the slow kinetics of hydrogen evolution reactions, oxygen evolution reactions, and large overpotentials. The anode with high performance for catalyzing hydrogen evolution reaction and the cathode with high performance for catalyzing oxygen evolution reaction can accelerate the reaction kinetics characteristic, thereby improving the performance of fuel cells and metal air cells. It is well known that Pt/C catalysts are highly efficient hydrogen evolution catalysts, IrO2/RuO2The catalyst is a high-efficiency oxygen precipitation catalyst, but has no prospect of large-scale application due to the problems of high price, scarce resources, poor stability and the like. Therefore, the search for electrode materials with low cost, high stability and bifunctional catalysis is currently the focus and focus of research in this field.
In addition, in the process of practical application and catalysis, in order to further improve the activity of the material: on one hand, the material is subjected to micro-nano treatment to form a nano-level structure, so that the electrochemical active area of the electrode material is increased to a certain extent, and the reaction is promoted. However, the conventional method for preparing the metal compound is a solid-phase method, and the method usually needs to be subjected to a high-temperature high-pressure heat treatment process, so that not only is the energy consumption high, but also the product size is generally large, and the nano-scale material cannot be obtained through control; on the other hand, the electrical conductivity of the catalyst is generally poor, and the method of adding conductive carbon is generally adopted to overcome the problem of low intrinsic electron conduction efficiency, but this causes the loss of active substances and causes some side reactions, which is also the key to limit the practical application of the catalyst as an electrode material. In addition, the traditional electrode preparation method is to mix and mechanically grind active substances, conductive carbon black, a binder and the like and then coat the mixture on a conductive substrate (such as carbon paper and carbon cloth). The integral electrode can expose more active sites, facilitating charge transport and gas diffusion. The foam nickel has good conductivity, and the nickel element has certain catalytic property and low price, and the like, so that the foam nickel is a catalyst substrate material which is well selected in the integrated electrode. There is a need for an inexpensive, highly active, integrated electrode that is catalytic. In addition, the homogeneous structure can reduce ohmic effects, reduce contact resistance, and improve the conductivity of the catalytic material.
The single atom concept is applied to the preparation of the electrocatalyst, so that the performance of the catalyst can be effectively improved, and the cost of the catalyst is reduced. In a monatomic catalyst, fully exposed atoms can increase the number of active sites; the low coordination unsaturation state and the enhanced metal support interaction can enhance the intrinsic activity of the active site. The synergistic promotion of the two aspects is beneficial to improving the performance of the catalyst. The high utilization rate of metal atoms can effectively reduce the cost of the catalyst. However, the monoatomic group is easy to migrate and agglomerate due to its large specific surface energy, so that it presents many challenges in synthesis. Designing a synthesis strategy to prepare a novel monatomic catalyst with high activity, high selectivity and high stability and researching the structure-activity relationship of the catalyst at atomic and molecular scales gradually attract the attention of researchers. Therefore, it is a very meaningful task to find a simple and feasible preparation method of the integrated electrode capable of generating the single atom.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides the nickel selenide sulfide nanorod coated by the tungsten-doped nickel selenide sulfide film growing on the surface of the foamed nickel, and the preparation method and the application thereof.
The purpose of the invention is realized by the following technical scheme.
The preparation method comprises the following steps of:
step 1, placing a selenium source in hydrazine hydrate, mechanically stirring and dissolving at the room temperature of 20-25 ℃ to obtain a selenium source mixed solution, wherein the concentration of the selenium source in the selenium source mixed solution is 2-12g/L (the selenium source is a solute and hydrazine hydrate is a solvent), adding thiourea, ammonium fluoride and a tungsten source into the selenium source mixed solution, then adding absolute ethyl alcohol and deionized water, and mechanically stirring at the room temperature of 20-25 ℃ to finally obtain a mixed solution, wherein the concentration of the thiourea in the mixed solution is 2-12g/L, the concentration of the ammonium fluoride is 4-16g/L, and the concentration of the tungsten source is 2-24g/L (the solvent is hydrazine hydrate, absolute ethyl alcohol and deionized water);
and 2, putting the mixed solution prepared in the step 1 and the foamed nickel into a reaction kettle for hydro-thermal treatment, wherein the reaction temperature is 120-260 ℃, the reaction time is 10-48h, cooling to the room temperature of 20-25 ℃, cleaning, drying, annealing in a protective atmosphere, the annealing temperature is 100-800 ℃, and the heat preservation time is 1-24h, so that the monatomic tungsten doped nickel selenide sulfide nanorod coated with the nickel selenide sulfide film growing on the surface of the foamed nickel is obtained.
In the step 1, the selenium source adopts one of selenium powder, selenium dioxide, selenocysteine or selenourea, the purity of the selenium source is 80.0-99.999%, the concentration is 5-8g/L, the purity of hydrazine hydrate is 80.0-98.0%, the mechanical stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
In the step 1, one of sodium tungstate, ammonium tungstate, tungsten trioxide or tungsten chloride is adopted as a tungsten source, the purity of thiourea is 80.0-99.0%, the concentration is 5-8g/L, the purity of ammonium fluoride is 80.0-99%, the concentration is 6-10g/L, the purity of the tungsten source is 80.0-99.9%, the concentration is 9-12g/L, the purity of absolute ethyl alcohol is 80.0-99.7%, and the volume ratio of the absolute ethyl alcohol solution to deionized water is 5: (5-1), the mechanical stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
Pretreatment of foamed nickel: and putting the foamed nickel into acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 5-40min, taking out, putting into an acid solution, soaking for 0.5-12h, putting into deionized water again, ultrasonically cleaning for 5-40min, and obtaining the pretreated foamed nickel.
In the step 2, the temperature of the hydrothermal reaction is 160-200 ℃, the reaction time is 16-24h, the drying temperature is 50-70 ℃, the drying time is 20-36h, the protective atmosphere adopts nitrogen, helium or argon, the annealing temperature is 160-250 ℃, and the heat preservation time is 2-8 h.
The sulfur nickel selenide nanorod coated by the monatomic tungsten-doped sulfur nickel selenide film growing on the surface of the foamed nickel is directly used as a full-electrolysis water integrated electrode, the hydrogen evolution overpotential of the sulfur nickel selenide nanorod coated by the monatomic tungsten-doped sulfur nickel selenide film growing on the surface of the foamed nickel is 50-82mV, the oxygen evolution overpotential is 270-330mV, and the full-electrolysis water overpotential is 1.55-1.65V.
The sulfur nickel selenide nanorod wrapped by the monatomic tungsten doped sulfur nickel selenide thin film growing on the surface of the foamed nickel directly serves as an electrode to directly form a full-hydrolytic device in an alkaline system without adding a conductive agent, a binder and an electrode preparation process, the sulfur nickel selenide nanorod wrapped by the monatomic tungsten doped sulfur nickel selenide thin film growing on the surface of the foamed nickel serves as a cathode working electrode and an anode working electrode at the same time, and a 1.0mol/L KOH aqueous solution serves as an electrolyte to form a full-hydrolytic system.
The invention has the beneficial effects that: the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film growing on the surface of the foamed nickel is uniform in appearance and consists of tungsten-nickel selenide sulfide and nickel selenide sulfide phases, the length of the nanorod is 1-6 mu m, the diameter of the nanorod is 100-300nm, the nanorod is uniformly distributed on the foamed nickel, and the unique microstructure is beneficial to exposure of active sites and increase of conductivity, so that the improvement of electrochemical performance is promoted; the preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production; the foamed nickel is used as a substrate to provide a three-dimensional conductive network channel, so that the obtained nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film on the surface of the foamed nickel can be directly used as an electrode for electrochemical performance test, other binders and conductive agents are not required to be additionally added, and the preparation process of the electrode is not required, so that the loading capacity of active substances is improved to the greatest extent. Meanwhile, the bonding force between the nickel selenide sulfide nanorod wrapped by the monatomic tungsten-doped nickel selenide sulfide film which grows in situ and the substrate is firm, the contact resistance is reduced, and the technical problem that the active substance is easy to fall off in the traditional process is solved. Thanks to the advantages, the electrode has excellent dual-function hydrogen evolution activity, oxygen evolution activity and stability in alkaline solution, and has wide application prospect in the aspects of full water decomposition and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a nickel selenide sulfide nanorod coated with a monatomic tungsten-doped nickel selenide sulfide thin film grown on the surface of a nickel foam prepared in the present invention;
FIG. 2 is a transmission electron microscope image of a nickel selenide sulfide nanorod coated with a monatomic tungsten-doped nickel selenide sulfide thin film grown on the surface of a nickel foam according to the present invention;
FIG. 3 is a transmission electron microscope image for spherical aberration correction of a nickel selenide sulfide nanorod coated with a monatomic tungsten-doped nickel selenide sulfide thin film grown on the surface of a nickel foam according to the present invention;
FIG. 4 is an XRD curve of the nickel selenide sulfide nanorod coated with the monatomic tungsten-doped nickel selenide sulfide thin film grown on the surface of the nickel foam;
FIG. 5 is XPS spectra of monatomic tungsten-doped nickel selenide thin film coated nickel selenide sulfide nanorods grown on a nickel foam surface made in the present invention;
FIG. 6 is an LSV diagram of HER in 1M KOH electrolyte of a nickel selenide sulfide nanorod coated with a monatomic tungsten-doped nickel selenide thin film grown on the surface of a nickel foam prepared in the present invention;
FIG. 7 is a graph of the results of long-cycle HER stability tests of a nickel selenide sulfide nanorod coated with a monatomic tungsten-doped nickel selenide thin film grown on a nickel foam surface in a 1M KOH electrolyte, according to the present invention;
FIG. 8 is an LSV diagram of OER of the nickel selenide sulfide nanorods wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film grown on the surface of the nickel foam in a 1M KOH electrolyte, prepared in the present invention;
FIG. 9 is a graph of the results of long-period OER stability tests of the single-atom tungsten-doped nickel selenide sulfide nanorod coated with the thin film of nickel selenide doped with sulfur grown on the surface of nickel foam in 1M KOH electrolyte according to the present invention;
FIG. 10 is a LSV diagram of total hydrolysis of a nickel selenide sulfide nanorod coated with a monatomic tungsten-doped nickel selenide sulfide thin film grown on the surface of a nickel foam in a 1M KOH electrolyte according to the present invention;
fig. 11 is a long-period full-hydrolysis stability test result diagram of the nickel selenide sulfide nanorod coated with the monatomic tungsten-doped nickel selenide sulfide thin film growing on the surface of the nickel foam, in the 1M KOH electrolyte.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Step 1, weighing 5.76g/L selenium powder, taking hydrazine hydrate solution with the concentration of 2.5mol/L to dissolve the selenium powder, at the moment, mechanically stirring at the rotating speed of 1200r/min for 30min at room temperature to obtain selenium source mixed solution, adding 5.56g/L thiourea, 8g/L ammonium fluoride and 11.13g/L tungsten trioxide into the selenium source mixed solution, then adding 4mol/L absolute ethyl alcohol with the concentration of 15mL and 9mL deionized water, and mechanically stirring at the rotating speed of 1200r/min at room temperature for 30min to obtain mixed solution;
and 3, pouring the mixed solution prepared in the step 1 into a reaction kettle with a polytetrafluoroethylene lining, putting the pretreated foamed nickel prepared in the step 2 into the reaction kettle, performing hydrothermal treatment, keeping the temperature at 180 ℃ for 20 hours, cooling, repeatedly washing with alcohol and ionized water, drying in an oven at 60 ℃ for 24 hours, annealing at 200 ℃ in an argon atmosphere for 2 hours, and obtaining the monatomic tungsten-doped nickel selenide sulfide film-coated nickel selenide sulfide nanorod growing on the surface of the foamed nickel.
As shown in FIG. 1, it is shown that the nickel selenide sulfide nanorods wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film are uniformly distributed on the nickel foam, the length of the nanorods is about 2 μm, and the diameter is about 150-180 nm.
As shown in FIG. 2, the synthesized nanorod structure is formed by densely wrapping a thin film outside a nanorod, the diameter of the nanorod is about 150-180nm, and the nanorod has a larger length-diameter ratio, so that the structure facilitates the exposure of active sites and is beneficial to the improvement of electrochemical performance.
As shown in fig. 3, the thin film of nickel selenide sulfur is shown to have monatomic tungsten doped into the nickel selenide sulfur.
As shown in fig. 4, the relative nickel selenide is shifted to a low angle, indicating that the tungsten is doped into the nickel selenide.
As shown in fig. 5, the material was shown to contain divalent nickel, sulfur and selenium, along with hexavalent tungsten, indicating that the composition of the sample was monoatomic tungsten doped nickel selenide sulfide.
The electrochemical performance testing instrument adopts Chenghua CHI760E electrochemical workstation, and the test performance analysis is as follows:
as shown in fig. 6, the monatomic tungsten-doped nickel selenide sulfide nanorod material wrapped by the nickel selenide sulfide thin film can reduce hydrogen evolution overpotential to below 54mV, and effectively reduce additional energy consumption.
As shown in FIG. 7, the material can still maintain a low overpotential after continuous catalytic hydrogen evolution for 100h in an alkaline environment, and is proved to have good stability.
As shown in FIG. 8, IrO is compared to the noble metal2The preparation method has the advantages that (the oxygen evolution overpotential is 330mV) is more excellent, the oxygen evolution overpotential can be reduced to be below 193mV by the nickel selenide sulfide nano rod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film, and the additional energy consumption is effectively reduced.
As shown in FIG. 9, the material can still maintain a low overpotential after continuous catalytic oxygen evolution for 100h in an alkaline environment, which indicates that the material has good stability.
As shown in FIG. 10, compared to the noble metal Pt/C (-) | IrO2The battery voltage of the nickel selenide sulfide film wrapped nano rod material can be reduced to below 1.47V, and the additional energy consumption is effectively reduced, wherein the Pt/C innochem accounts for 99.99 percent of Pt 20 percent, and the IrO2innochem 99.99％Ir 84.5％。
As shown in FIG. 11, the material can still maintain a low potential after continuously catalyzing full-hydrolysis in an alkaline environment for 100h, which indicates good stability.
Example 2
Step 1, weighing selenium dioxide with the concentration of 2.88g/L, taking hydrazine hydrate solution with the concentration of 1.5mol/L to dissolve the selenium dioxide, at the moment, mechanically stirring at the rotating speed of 600r/min for 20min at room temperature to obtain selenium source mixed solution, adding thiourea with the concentration of 8.34g/L, ammonium fluoride with the concentration of 10g/L and sodium tungstate with the concentration of 2g/L into the selenium source mixed solution, then adding 12mL of absolute ethyl alcohol with the concentration of 3mol/L and 15mL of deionized water, and mechanically stirring at the rotating speed of 600r/min at room temperature for 20min to obtain mixed solution;
step 3, pouring the mixed solution prepared in the step 1 into a reaction kettle with a 50ml polytetrafluoroethylene lining, putting the foamed nickel pretreated in the step 2 into the reaction kettle, putting the reaction kettle into an oven, and preserving heat for 48 hours at 120 ℃; and after cooling, repeatedly washing with alcohol and ionized water, drying in an oven for 48h at 40 ℃, annealing and preserving heat for 24h at 100 ℃ in the nitrogen atmosphere, and obtaining the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide nano rod material by scanning, a transmission electron microscope, a spherical aberration correction transmission electron microscope, XRD and XPS are utilized to obtain the monoatomic tungsten doped nickel selenide sulfide nano rod material growing on the surface of the foamed nickel and wrapped by the nickel selenide sulfide thin film. The nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film prepared in the embodiment is composed of monatomic tungsten-doped nickel selenide sulfide and nickel selenide sulfide, the length of the nanorod is 1 mu m, the diameter of the nanorod is 100-120nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve diagram of the monatomic tungsten-doped nickel selenide sulfide nanorod material wrapped by the nickel selenide sulfide thin film in the 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film is about 54mV, the oxygen evolution overpotential is about 300mV, and the total hydrolysis water potential is about 1.58V, so that the extra energy consumption is effectively reduced, and the stability is good.
Example 3
Step 1, weighing 8.64g/L selenocysteine, taking hydrazine hydrate solution with the concentration of 5mol/L to dissolve the selenocysteine, at the moment, mechanically stirring at the rotating speed of 1600r/min for 40min at room temperature to obtain selenium source mixed solution, adding 2.78g/L thiourea, 10mol/L ammonium fluoride and 2g/L ammonium tungstate into the selenium source mixed solution, then adding 6mol/L absolute ethanol and 5mL deionized water with the concentration of 15mL, and mechanically stirring at the rotating speed of 1600r/min for 40min at room temperature to obtain mixed solution;
and 3, pouring the mixed solution prepared in the step 1 into a 50ml reaction kettle with a polytetrafluoroethylene lining, putting the foamed nickel pretreated in the step 2 into the reaction kettle, putting the reaction kettle into an oven, keeping the temperature at 260 ℃ for 10h, cooling, repeatedly washing with alcohol and ionized water, drying in the oven at 100 ℃ for 6h, annealing at 800 ℃ in a helium atmosphere, keeping the temperature for 1h, and obtaining the monatomic tungsten doped nickel selenide sulfide nano rod material wrapped by the thin film of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide nano rod material by scanning, a transmission electron microscope, a spherical aberration correction transmission electron microscope, XRD and XPS are utilized to obtain the monoatomic tungsten doped nickel selenide sulfide nano rod material growing on the surface of the foamed nickel and wrapped by the nickel selenide sulfide thin film. The nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film prepared in the embodiment is composed of monatomic tungsten-doped nickel selenide sulfide and nickel selenide sulfide, the length of the nanorod is 3 micrometers, the diameter of the nanorod is 270-300 nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve diagram of the monatomic tungsten-doped nickel selenide sulfide nanorod material wrapped by the nickel selenide sulfide thin film in the 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film is about 74mV, the oxygen evolution overpotential is about 320mV, and the total hydrolysis water potential is about 1.62V, so that the extra energy consumption is effectively reduced, and the stability is good.
Example 4
Step 1, weighing selenourea with the concentration of 2g/L, taking hydrazine hydrate solution with the concentration of 1mol/L to dissolve selenourea, at the moment, mechanically stirring at the rotating speed of 1500r/min for 25min at room temperature to obtain selenium source mixed solution, adding thiourea with the concentration of 12g/L, ammonium fluoride with the concentration of 16g/L and tungsten chloride with the concentration of 24g/L into the selenium source mixed solution, then adding 13mL of absolute ethyl alcohol with the concentration of 2mol/L and 15mL of deionized water, and mechanically stirring at the rotating speed of 1500r/min at room temperature for 25min to obtain mixed solution;
and 3, pouring the mixed solution prepared in the step 1 into a reaction kettle with a 50ml polytetrafluoroethylene lining, putting the foamed nickel pretreated in the step 2 into the reaction kettle, putting the reaction kettle into an oven, keeping the temperature at 260 ℃ for 10 hours, cooling, repeatedly washing with alcohol and ionized water, drying in the oven at 80 ℃ for 18 hours, annealing at 400 ℃ in an argon atmosphere, and keeping the temperature for 10 hours to obtain the monatomic tungsten doped nickel selenide sulfide film coated nickel selenide nano rod material growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide nano rod material by scanning, a transmission electron microscope, a spherical aberration correction transmission electron microscope, XRD and XPS are utilized to obtain the monoatomic tungsten doped nickel selenide sulfide nano rod material growing on the surface of the foamed nickel and wrapped by the nickel selenide sulfide thin film. The nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film prepared in the embodiment is composed of monatomic tungsten-doped nickel selenide sulfide and nickel selenide sulfide, the length of the nanorod is 1.5 mu m, the diameter of the nanorod is 100-120nm, and the nanorod is uniformly distributed on nickel foam.
The polarization curve diagram of the monatomic tungsten-doped nickel selenide sulfide nanorod material wrapped by the nickel selenide sulfide thin film in the 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film is about 62mV, the oxygen evolution overpotential is about 280mV, and the total hydrolysis water potential is about 1.57V, so that the extra energy consumption is effectively reduced, and the stability is good.
Example 5
Step 1, weighing 12g/L selenium powder, taking hydrazine hydrate solution with the concentration of 5mol/L to dissolve the selenium powder, at the moment, mechanically stirring at the rotating speed of 2000r/min for 60min at room temperature to obtain selenium source mixed solution, adding thiourea with the concentration of 2g/L, ammonium fluoride with the concentration of 4g/L and tungsten trioxide with the concentration of 15g/L into the selenium source mixed solution, adding 10mL of absolute ethyl alcohol with the concentration of 8mol/L and 10mL of deionized water, and mechanically stirring at the rotating speed of 2000r/min at room temperature for 60min to obtain mixed solution;
and 3, pouring the mixed solution prepared in the step 1 into a reaction kettle with a 50ml polytetrafluoroethylene lining, putting the foamed nickel pretreated in the step 2 into the reaction kettle, putting the reaction kettle into a drying oven, preserving heat for 48 hours at 160 ℃, repeatedly washing with alcohol and ionized water after cooling, drying for 36 hours at 30 ℃ in the drying oven, annealing and preserving heat for 15 hours at 400 ℃ in an argon atmosphere, and obtaining the monatomic tungsten doped nickel selenide sulfide film coated nickel selenide nanorod material growing on the surface of the foamed nickel.
The characterization results of the morphology and the structure of the nickel selenide nano rod material by scanning, a transmission electron microscope, a spherical aberration correction transmission electron microscope, XRD and XPS are utilized to obtain the monoatomic tungsten doped nickel selenide sulfide nano rod material growing on the surface of the foamed nickel and wrapped by the nickel selenide sulfide thin film. The nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film prepared in the embodiment is composed of monatomic tungsten-doped nickel selenide sulfide and nickel selenide sulfide, the length of the nanorod is 6 microns, the diameter of the nanorod is 260-300nm, and the nanorod is uniformly distributed on the nickel foam.
The polarization curve diagram of the monatomic tungsten-doped nickel selenide sulfide nanorod material wrapped by the nickel selenide sulfide thin film in the 1M KOH electrolyte is that the hydrogen evolution overpotential of the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide thin film is about 80mV, the oxygen evolution overpotential is about 324mV, and the total hydrolysis water potential is about 1.63V, so that the extra energy consumption is effectively reduced, and the stability is good.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The nickel selenide sulfide nanorod coated by the tungsten-doped nickel selenide sulfide film growing on the surface of the nickel foam is characterized in that: the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film is composed of tungsten-nickel selenide sulfide and nickel selenide sulfide phases, the length of the nickel selenide sulfide nanorod is 1-6 mu m, the diameter of the nickel selenide sulfide nanorod is 100-300nm, the thickness of the monatomic tungsten-doped nickel selenide sulfide film is 1-10nm, the nickel selenide sulfide nanorod wrapped by the monatomic tungsten-doped nickel selenide sulfide film is uniformly distributed on the foamed nickel, and the method comprises the following steps:
step 1, placing a selenium source in hydrazine hydrate, mechanically stirring and dissolving at the room temperature of 20-25 ℃ to obtain a selenium source mixed solution, wherein the concentration of the selenium source in the selenium source mixed solution is 2-12g/L, adding thiourea, ammonium fluoride and a tungsten source into the selenium source mixed solution, then adding absolute ethyl alcohol and deionized water, and mechanically stirring at the room temperature of 20-25 ℃ to finally obtain a mixed solution, wherein the concentration of thiourea in the mixed solution is 2-12g/L, the concentration of ammonium fluoride is 4-16g/L, and the concentration of the tungsten source is 2-24 g/L;
and 2, putting the mixed solution prepared in the step 1 and the foamed nickel into a reaction kettle for hydro-thermal treatment, wherein the reaction temperature is 120-260 ℃, the reaction time is 10-48h, cooling to the room temperature of 20-25 ℃, cleaning, drying, annealing in a protective atmosphere, the annealing temperature is 100-800 ℃, and the heat preservation time is 1-24h, so that the monatomic tungsten doped nickel selenide sulfide nanorod coated with the nickel selenide sulfide film growing on the surface of the foamed nickel is obtained.
2. The nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 1, wherein: in the step 1, the selenium source is one of selenium powder, selenium dioxide, selenocysteine or selenourea, the purity of the selenium source is 80.0-99.999%, the concentration is 5-8g/L, the purity of hydrazine hydrate is 80.0-98.0%, the mechanical stirring speed is 600-2000r/min, the stirring time is 20-60min, the tungsten source is one of sodium tungstate, ammonium tungstate, tungsten trioxide or tungsten chloride, the purity of thiourea is 80.0-99.0%, the concentration is 5-8g/L, the purity of ammonium fluoride is 80.0-99%, the concentration is 6-10g/L, the purity of tungsten source is 80.0-99.9%, the concentration is 9-12g/L, the purity of absolute ethyl alcohol is 80.0-99.7%, the volume ratio of the absolute ethyl alcohol solution to the deionized water is 5: (5-1), the mechanical stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
3. The nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 1, wherein: pretreatment of foamed nickel: and putting the foamed nickel into acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 5-40min, taking out, putting into an acid solution, soaking for 0.5-12h, putting into deionized water again, ultrasonically cleaning for 5-40min, and obtaining the pretreated foamed nickel.
4. The nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 1, wherein: in the step 2, the temperature of the hydrothermal reaction is 160-200 ℃, the reaction time is 16-24h, the drying temperature is 50-70 ℃, the drying time is 20-36h, the protective atmosphere adopts nitrogen, helium or argon, the annealing temperature is 160-250 ℃, and the heat preservation time is 2-8 h.
5. The preparation method of the nickel selenide sulfide nanorod coated by the tungsten-doped nickel selenide sulfide film growing on the surface of the nickel foam is characterized in that: the nickel selenide sulfide nanorod material wrapped by the monatomic tungsten-doped nickel selenide sulfide film is composed of tungsten-nickel selenide sulfide and nickel selenide sulfide phases, the length of the nickel selenide sulfide nanorod is 1-6 mu m, the diameter of the nickel selenide sulfide nanorod is 100-300nm, the thickness of the monatomic tungsten-doped nickel selenide sulfide film is 1-10nm, the nickel selenide sulfide nanorod wrapped by the monatomic tungsten-doped nickel selenide sulfide film is uniformly distributed on the foamed nickel, and the method comprises the following steps:
step 1, placing a selenium source in hydrazine hydrate, mechanically stirring and dissolving at the room temperature of 20-25 ℃ to obtain a selenium source mixed solution, wherein the concentration of the selenium source in the selenium source mixed solution is 2-12g/L, adding thiourea, ammonium fluoride and a tungsten source into the selenium source mixed solution, then adding absolute ethyl alcohol and deionized water, and mechanically stirring at the room temperature of 20-25 ℃ to finally obtain a mixed solution, wherein the concentration of thiourea in the mixed solution is 2-12g/L, the concentration of ammonium fluoride is 4-16g/L, and the concentration of the tungsten source is 2-24 g/L;
and 2, putting the mixed solution prepared in the step 1 and the foamed nickel into a reaction kettle for hydro-thermal treatment, wherein the reaction temperature is 120-260 ℃, the reaction time is 10-48h, cooling to the room temperature of 20-25 ℃, cleaning, drying, annealing in a protective atmosphere, the annealing temperature is 100-800 ℃, and the heat preservation time is 1-24h, so that the monatomic tungsten doped nickel selenide sulfide nanorod coated with the nickel selenide sulfide film growing on the surface of the foamed nickel is obtained.
6. The method for preparing nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 5, wherein the method comprises the following steps: in the step 1, the selenium source adopts one of selenium powder, selenium dioxide, selenocysteine or selenourea, the purity of the selenium source is 80.0-99.999%, the concentration is 5-8g/L, the purity of hydrazine hydrate is 80.0-98.0%, the mechanical stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
7. The method for preparing nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 5, wherein the method comprises the following steps: in the step 1, one of sodium tungstate, ammonium tungstate, tungsten trioxide or tungsten chloride is adopted as a tungsten source, the purity of thiourea is 80.0-99.0%, the concentration is 5-8g/L, the purity of ammonium fluoride is 80.0-99%, the concentration is 6-10g/L, the purity of the tungsten source is 80.0-99.9%, the concentration is 9-12g/L, the purity of absolute ethyl alcohol is 80.0-99.7%, and the volume ratio of the absolute ethyl alcohol solution to deionized water is 5: (5-1), the mechanical stirring speed is 600-2000r/min, and the stirring time is 20-60 min.
8. The method for preparing nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 5, wherein the method comprises the following steps: pretreatment of foamed nickel: and putting the foamed nickel into acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 5-40min, taking out, putting into an acid solution, soaking for 0.5-12h, putting into deionized water again, ultrasonically cleaning for 5-40min, and obtaining the pretreated foamed nickel.
9. The method for preparing nickel selenide sulfide nanorods wrapped by tungsten doped nickel selenide sulfide thin film grown on the surface of nickel foam according to claim 5, wherein the method comprises the following steps: in the step 2, the temperature of the hydrothermal reaction is 160-200 ℃, the reaction time is 16-24h, the drying temperature is 50-70 ℃, the drying time is 20-36h, the protective atmosphere adopts nitrogen, helium or argon, the annealing temperature is 160-250 ℃, and the heat preservation time is 2-8 h.
10. The use of the nickel selenide sulfide nanorods coated with the tungsten doped nickel selenide sulfide thin film grown on the surface of the nickel foam according to any one of claims 1 to 4 in the electrolysis of water, wherein: the nickel selenide sulfide nanorod coated by the monatomic tungsten-doped nickel selenide sulfide film growing on the surface of the nickel foam can be directly applied to the integrated electrode for total hydrolysis, and simultaneously used as a cathode and an anode, the nickel selenide sulfide nanorod coated by the monatomic tungsten-doped nickel selenide sulfide film growing on the surface of the nickel foam has the hydrogen evolution overpotential of 50-82mV, the oxygen evolution overpotential of 270-330mV, and the water electrolysis potential of 1.55-1.65V.
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