CN113151857A - Two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet and preparation method and application thereof - Google Patents
Two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet and preparation method and application thereof Download PDFInfo
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- CN113151857A CN113151857A CN202110336163.7A CN202110336163A CN113151857A CN 113151857 A CN113151857 A CN 113151857A CN 202110336163 A CN202110336163 A CN 202110336163A CN 113151857 A CN113151857 A CN 113151857A
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 129
- 239000002135 nanosheet Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 238000000464 low-speed centrifugation Methods 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000703 high-speed centrifugation Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002390 adhesive tape Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 10
- 239000010406 cathode material Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 transition metal chalcogenide compound Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
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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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to the technical field of nano material preparation, in particular to a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) taking molybdenum disulfide powder as a working electrode, and electrochemically stripping in N, N-dimethylformamide electrolyte containing nickel salt and electrolyte to obtain nickel-doped molybdenum disulfide; (2) filtering and collecting nickel-doped molybdenum disulfide, washing, drying and then carrying out ultrasonic treatment in a dispersion solution; (3) and carrying out centrifugal separation and freeze drying on the suspension subjected to ultrasonic treatment to obtain the nickel-doped molybdenum disulfide nanosheet. The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet prepared by the method has the average thickness of not more than 5nm, has the advantages of ultrathin layered structure, uniform thickness and good crystallinity, is used for electrolyzing water cathode materials, and has excellent electrochemical hydrogen evolution performance and good stability in alkaline solution.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet and a preparation method and application thereof.
Background
Hydrogen is abundant on earth, and hydrogen energy has very high energy density, so that the hydrogen energy is an ideal choice for replacing traditional fossil fuels in the future. Compared with other technologies for preparing hydrogen energy, such as biological hydrogen production, chemical fuel hydrogen production and water electrolysis hydrogen production, the method has the characteristics of high efficiency and cleanness.
At present, noble metal platinum-based catalysts are the most efficient hydrogen-generating electrocatalysts, but the shortage of the content and the higher cost limit the large-scale application of the noble metal platinum-based catalysts in industry. Transition metal binary compounds (TMDs) are a class of layered materials that are widely used due to their unique electronic, mechanical, catalytic, and electrochemical properties. In recent years, researchers have found that single or few layers of transition metal binary compounds exhibit interesting characteristics that are not present in their bulk counterparts. Molybdenum sulfide is a typical two-dimensional transition metal chalcogenide compound, and due to its two-dimensional structure and unique physicochemical properties, it exhibits excellent electrochemical hydrogen evolution performance when its size is reduced to the nano-scale and exfoliated into single-layer nanosheets. It is therefore of great interest to develop an effective method for stripping a molybdenum disulfide layer without compromising its structural integrity, thereby maintaining its particular properties.
At present, the two-dimensional ultrathin molybdenum disulfide nanosheets are prepared by a lithium ion intercalation method, a liquid phase ultrasonic stripping method, a mechanical stripping method and the like.
For example, in patent publication No. CN103833081A, molybdenum disulfide nanosheets prepared by intercalating molybdenum disulfide powder with lithium ions and then preparing molybdenum disulfide nanosheets with a thickness of from a single layer to several layers by hydrolysis and ultrasonic treatment have good quality. But because of the need of anhydrous and oxygen-free environment during the intercalation treatment of lithium ions in the preparation process, the method is not suitable for industrial mass production.
The liquid phase ultrasonic stripping method is to intercalate the bulk material with solvent molecules through an ultrasonic process, thereby realizing the stripping of the material into a flake form. For example, in patent publication No. CN 107364890a, polyaniline conductive polymer and molybdenum disulfide powder are uniformly mixed in water or organic solvent, and then two-dimensional molybdenum disulfide nanosheets are obtained by physical means such as ultrasound and oscillation. Although the liquid phase ultrasonic stripping method has simple steps and operation, the quality of the product is not easy to control, and the method also has the problems of long treatment time and low efficiency, and is not suitable for mass production.
There are also two-dimensional material preparation methods such as mechanical lift-off, chemical vapor deposition, and the like. Due to the high cost and the difficult operation, the methods are not suitable for industrial mass production.
Therefore, the preparation method of the cathode hydrogen evolution material which is simple to operate, low in cost, high in product quality and suitable for large-scale industrial production and application is designed, and has great significance for meeting the requirement of large-scale water electrolysis hydrogen production in the future, further enabling hydrogen to be popularized and used in daily life and solving the energy and environmental problems.
Disclosure of Invention
The invention aims to overcome the problems that a two-dimensional material stripping method in the prior art is not enough, is not suitable for mass production and the prepared catalyst is not ideal in effect, and provides a preparation method of a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet, which is low in production cost, high in product catalysis efficiency and suitable for large-scale production, and has certain significance for further development of hydrogen energy and solving of energy and environment problems.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet comprises the following steps:
(1) fixing molybdenum disulfide powder on a copper adhesive tape through conductive silver adhesive to serve as a working electrode, and electrochemically stripping in N, N-dimethylformamide electrolyte containing nickel salt and electrolyte to obtain nickel-doped molybdenum disulfide;
(2) filtering and collecting nickel-doped molybdenum disulfide in the electrolyte, washing and drying the nickel-doped molybdenum disulfide, and performing ultrasonic treatment in a dispersion solution;
(3) and carrying out centrifugal separation and freeze drying on the suspension subjected to ultrasonic treatment to obtain the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet.
According to the invention, nickel element is doped into the product while the molybdenum disulfide powder is stripped by adopting an electrochemical method, and before voltage is applied, the molybdenum disulfide powder is a bulk block which is a structure with laminated layers. Electrolyte and Ni in the electrolyte when negative voltage is applied to the working electrode+And N, N-Dimethylformamide (DMF) solution forming complex permeates into the layers of the bulk molybdenum disulfide, and van der Waals force between the layers of the molybdenum disulfide is slowly overcome, so that the molybdenum disulfide layers are separated from each other, and meanwhile, Ni+The preparation method has the advantages that the preparation method is low in required cost, high in product quality, simple and efficient, and suitable for large-scale production.
The molybdenum disulfide powder can be a commercially available product, and can also be prepared by the following preparation method, which comprises the following steps: and grinding the sulfur powder and the molybdenum powder, sealing the ground sulfur powder and molybdenum powder in a vacuum quartz glass tube, heating the mixture for 2-5 hours at 900-1000 ℃, and cooling to obtain the molybdenum disulfide powder. The temperature rise rate is usually 1 to 10 ℃/min. Because the performance of the molybdenum disulfide powder purchased in a market place is unstable, the nickel-doped molybdenum disulfide nanosheet obtained from the molybdenum disulfide powder self-prepared by the method has better application effect.
The nickel salt is soluble salt, including any one of nickel chloride, nickel acetate, nickel sulfate and nickel nitrate. Preferably, the nickel salt is nickel chloride, and the inventors have found through experiments that the thickness of the nickel chloride is more uniform and the electrocatalytic effect is better than that of molybdenum disulfide nanosheets prepared from other nickel salts.
The electrolyte comprises any one of tetrabutylammonium bromide, tetrapropylammonium bromide and tetraethylammonium bromide. The electrolyte forms a complex with nickel ions and DMF solution in the electrolyte and enters the molybdenum disulfide lamella (the interlayer spacing is 0.62nm) to promote the stripping of the molybdenum disulfide, so that the selection of the electrolyte with proper molecular size plays a very important role in the stripping effect, wherein TBA in tetrabutylammonium bromide+Ion size of 0.89nm, TPA in tetrapropylammonium bromide+Ion size of 0.67nm, TEA in tetraethylammonium bromide+The ion size was 0.56 nm. Preferably, the electrolyte is tetrabutylammonium bromide.
The magnitude of the applied negative voltage and the duration of the applied voltage that is maintained are the most critical functions in producing high quality nickel doped molybdenum disulfide flakes. The negative voltage of the electrochemical stripping in the step (1) is-1 to-10V; the time of electrochemical stripping is 20-40 min. The stripping quality of the molybdenum disulfide is not high due to the fact that the negative voltage is applied excessively, the obtained nickel-doped molybdenum disulfide flake is thick, the stripping efficiency is low due to the fact that the negative voltage is applied slightly, and the yield of the obtained nickel-doped molybdenum disulfide flake is low. Therefore, it is necessary to select a proper applied voltage, so that high-quality and high-yield nickel-doped molybdenum disulfide flakes can be obtained in the stripping process. Preferably, the electrochemical stripping time is 25-35 min, and most preferably, the electrochemical stripping time is 30 min.
In the step (1), the counter electrode is made of a foil, the counter electrode and the working electrode are placed in parallel at a distance of 1-3 cm, and the stripping rate and the heat effect balance of the molybdenum disulfide can be controlled.
In the step (2), the aperture of the filter membrane used for filtration is not more than 0.2 μm, so that molybdenum disulfide particles can be better removed, and stripped molybdenum disulfide flakes are ensured in the ultrasonic solution.
The power of ultrasonic treatment in the step (2) is 300-500W, and the time is 1-2 h. TBA in the course of electrochemical stripping+Ion and TBA+The complex formed by the ions and DMF enters the layers of the molybdenum disulfide together, and the van der Waals force between the layers is broken. Subsequent ultrasonic treatment can make the molybdenum disulfide flake layer open more greatly, can obtain the molybdenum disulfide flake of even dispersion finally. The molybdenum disulfide flake is broken to a large extent due to large ultrasonic power and time, and the molybdenum disulfide flake is stacked together due to small ultrasonic power and time and cannot be uniformly dispersed. The quality of the nano-sheets obtained by the treatment with the ultrasonic power of 500W and the time of 2 hours is the best. Wherein each ultrasonic operation is suspended for a period of time, such as 1s of operation and 0.5s of suspension, so as to prevent the ultrasonic crushing instrument from overheating.
And (3) selecting an organic solvent which can be mutually dissolved with water in the dispersion solution in the step (2), wherein the organic solvent comprises N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like, and the dispersion solution can influence the stripping efficiency and the product quality, wherein the N, N-dimethylformamide organic solvent is used as the stripping solution, and the prepared molybdenum disulfide sheet has the best quality.
The centrifugal separation of the suspension in the step (3) adopts a low-speed centrifugation and high-speed centrifugation method, and specifically comprises the following steps:
(1) low-speed centrifugation: rotating at 2000-4000 rpm for 20-30 min, and collecting supernatant;
(2) high-speed centrifugation: rotating at 8000-12000 rpm, centrifuging for 20-30 min, and collecting precipitate;
(3) washing: and washing the precipitate for 1-3 times by adopting absolute ethyl alcohol and water respectively, wherein the centrifugal rotation speed is 8000-12000 rpm, and the centrifugal time is 20-30 min.
The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet with higher quality can be obtained by high-speed and low-speed stepwise centrifugal treatment. In the low-speed centrifugation process, part of molybdenum disulfide nanosheets with larger thickness, larger particles or uneven layering are deposited on the lower layer, so that supernatant is taken in the low-speed centrifugation process, wherein the molybdenum disulfide nanosheets with smaller thickness and even layering are mainly in the supernatant; in the high-speed centrifugation process, trace impurities, molybdenum disulfide powder which is not flaky and the like are separated out through rapid rotation centrifugation, and the molybdenum disulfide nanosheet with uniform thickness and average thickness not more than 5nm is obtained.
The invention also provides the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet prepared by the preparation method, and the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet is characterized in that the average thickness of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet is not more than 5 nm. In the preparation process, the voltage and time of the electrochemical stripping process, the later ultrasonic time, the centrifugal process and the like are comprehensively controlled, so that the finally obtained nickel-doped molybdenum disulfide nanosheet is uniform in thickness, the average thickness is not more than 3.5nm, the ultrathin lamellar structure nanosheet is good in crystallization performance, and the electrochemical hydrogen evolution performance is excellent in application.
The invention also provides application of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet in electrochemical hydrogen evolution. The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet is used as an electrolytic water cathode material, and has excellent electrochemical hydrogen evolution performance and good stability in an alkaline solution. When the current density is 10mA cm-2In the process, the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet material disclosed by the invention shows excellent overpotential-145 mV in a three-electrode alkaline solution test, and in a stability test, the current change of the catalyst is small when the constant voltage is kept for 7200s, so that the catalyst has good stability.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a preparation method of a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet, which is characterized in that molybdenum disulfide powder is stripped by adopting an electrochemical method, nickel elements are doped into the product, and the preparation of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet by a one-step method is realized.
(2) The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet prepared by the method has the average thickness of not more than 5nm, has the advantages of ultrathin layered structure, uniform thickness and good crystallinity, is used for electrolyzing water cathode materials, and has excellent electrochemical hydrogen evolution performance and good stability in alkaline solution.
Drawings
Fig. 1 is a TEM image of a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet prepared in example 1, and the inset is a selected area diffraction image SAED.
Fig. 2 is an AFM image of the two-dimensional ultra-thin nickel-doped molybdenum disulfide nanosheet prepared in example 1.
Fig. 3 is an XRD pattern of the two-dimensional ultra-thin nickel-doped molybdenum disulfide nanosheet prepared in example 1.
Fig. 4 is a polarization curve diagram of the hydrogen evolution reaction by electrolysis and water of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet prepared in example 1.
Fig. 5 is a graph showing the change of current with time under constant voltage in the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet electrolyzed water hydrogen evolution prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
The raw materials used in the following embodiments are all commercially available.
Example 1
1. Preparation of molybdenum disulfide powder
(1) Mixing sulfur powder and molybdenum powder according to a stoichiometric ratio, fully grinding, and sealing the mixture in a vacuum quartz glass tube;
(2) and (3) heating the mixture by using a tubular furnace from room temperature, wherein the heating temperature is 950 ℃, the holding time is 5h, the heating rate is 5 ℃/min, and naturally cooling after heating is finished to obtain the molybdenum disulfide powder.
2. Preparation of the electrolyte
(1) About 50mL of N, N-dimethylformamide is weighed, 1g of tetrabutylammonium bromide and 0.6g of nickel chloride hexahydrate are weighed, dissolved and stirred by the N, N-dimethylformamide, and the volume is determined in a 100mL volumetric flask to obtain the electrolyte.
3. Electrochemical stripping of molybdenum disulfide powder
(1) Bonding molybdenum disulfide powder on a copper adhesive tape by using conductive silver adhesive to be connected with an electrode, wherein the copper adhesive tape is used as a working electrode, a 1.5 cm-by-1.5 cm platinum sheet is used as a counter electrode, N-dimethylformamide solution containing tetrabutylammonium bromide and nickel chloride is used as electrolyte, and the counter electrode and the working electrode are placed in the electrolyte at a distance of 2 cm;
(2) applying-10V voltage to the working electrode, and keeping for 30 min;
4. stripping off nickel-doped molybdenum disulfide flake for cleaning
(1) The electrolyte containing nickel-doped molybdenum disulfide flakes was vacuum filtered with a 0.25 μm pore size teflon filter and rinsed multiple times with ultrapure water, and the flakes were collected and redispersed in N, N-dimethylformamide solvent.
5. Ultrasonic treatment
(1) And carrying out ultrasonic crushing treatment on the dispersion liquid containing the nickel-doped molybdenum disulfide flakes. The ultrasonic power is 500W, the ultrasonic time is 2h, wherein the ultrasonic work is 1s, and the ultrasonic pause is 0.5 s.
6. Centrifugal treatment step by step
(1) Centrifuging the dispersion liquid containing the nickel-doped molybdenum disulfide flakes after the ultrasonic treatment, setting the low-speed centrifugation rotation speed to be 4000rpm, centrifuging for 30min, and taking supernatant;
(2) centrifuging the supernatant at high speed of 10000rmp for 30min to obtain precipitate;
(3) washing the precipitate with ultrapure water and anhydrous ethanol for 3 times respectively, centrifuging at 10000rpm for 30min, and collecting the precipitate.
7. Freeze drying process
And (4) carrying out freeze drying treatment on the precipitate obtained in the step (6) to obtain the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet. The nanosheets are observed by a transmission electron microscope, and the result is shown in fig. 1, wherein an inset is a selected area diffraction image SAED, and thus the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets are in an ultrathin layered structure. AFM of molybdenum disulfide nanosheets As shown in FIG. 2, the average thickness of two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets was measured to be about 3.5 nm. The X-ray diffraction XRD of the nickel-doped molybdenum disulfide nanosheet is shown in figure 3, and it can be seen that the components of molybdenum disulfide are not changed by the electrochemical stripping method.
Examples 2 to 3
According to the preparation process of the embodiment 1, the stripping voltage in the step 3 is respectively changed to-5V and-15V, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under the conditions of different stripping voltages are obtained.
Examples 4 to 5
According to the preparation process of the embodiment 1, the time for stripping in the step 3 is changed to 10min and 45min respectively, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under the conditions of different stripping times are obtained.
Examples 6 to 7
According to the preparation process of the embodiment 1, the ultrasonic power in the step 5 is respectively changed to 300W and 600W, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under the conditions of different ultrasonic powers are obtained.
Examples 8 to 9
According to the preparation process of the embodiment 1, the ultrasonic time in the step 5 is changed to 1 hour and 3 hours respectively, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different ultrasonic time conditions are obtained.
Examples 10 to 11
According to the preparation process of the embodiment 1, the nickel salt in the step 2 is changed into nickel sulfate and nickel nitrate respectively, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different nickel salt conditions are obtained.
Application example 1 three-electrode System for electrochemical Hydrogen evolution
(1) A three-electrode system is used, the working electrode is the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet of example 1, the counter electrode is a carbon rod, the reference electrode is a saturated silver/silver chloride electrode, and the electrolyte is a 1M potassium hydroxide solution;
(2) CV activation: the electrochemical workstation of Shanghai Chenghua CHI 660E was used, and nitrogen was introduced into the electrolyte for 30min before the test. Adopting CV program, testing interval at 0-0.8V vs. RHE, sweeping speed at 50mV/s, circulating for 30 circles, and making the electrode reach stable state.
(3) Linear Sweep Voltammetry (LSV) test: after CV activation, the switching program is LSV program, the test interval is 0-0.8V vs. RHE, and the sweep rate is 5 mV/s. The polarization curve is shown in FIG. 4, and it can be observed that the overpotential of the catalyst in the alkaline solution is-145 mV.
(4) And (3) stability testing: after CV activation, the program was switched to i-t program, voltage was set to-0.3V (vs. rhe), and time was set to 7200 s. The current curve with time at constant voltage is shown in fig. 5, and the current of the catalyst does not change much, demonstrating its good stability.
The embodiment shows that the obtained two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet has excellent electrochemical performance and good stability in alkaline solution as an electrolytic water cathode material. The hydrogen reduction performance of two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different stripping conditions in alkaline solution is listed in table 1.
TABLE 1 Performance of catalysts of application examples 1-11
As can be seen from Table 1, the current density of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different conditions in the application examples 2-11 in the alkaline solution reaches 10 mA-cm-2The overpotential in time is greater than application example 1. Application examples 2 to 3 compare with application example 1, the negative voltage applied during electrochemical strippingDriving TBA+Ions enter the interlayer of the molybdenum disulfide, and the voltage is applied too little to cause TBA+The quantity of ions embedded into the molybdenum disulfide layers is small, the intervals among the molybdenum disulfide layers cannot be opened, the prepared product is thicker, and the electrocatalytic performance is lower; too large of a voltage application results in TBA+The quantity of ions embedded into the molybdenum disulfide layers is too large, the molybdenum disulfide thin layers are seriously damaged, the quality of the obtained product is not high, and the electrocatalytic performance is low.
Application examples 4 to 5 compare with application example 1, and TBA was introduced as the time of application in electrochemical stripping+The amount of ions entering the interlayer of the molybdenum disulfide is a key factor. TBA+The molybdenum disulfide thin layer is seriously damaged due to excessive ions, and the prepared product has low quality and weaker electro-catalysis performance; TBA+The van der Waals force between the molybdenum disulfide layers cannot be broken due to the small quantity of ions, and the prepared product is thick and has low electro-catalytic performance.
Application examples 6-9 compare with application example 1, and the product that the electrochemistry was peeled off obtains, and in the supersound process, the size of its power has very big influence to the dispersion degree of molybdenum disulfide thin layer, and wherein ultrasonic power and time are great can lead to the broken degree of molybdenum disulfide thin layer big, and ultrasonic power and time are less can lead to the molybdenum disulfide thin layer to pile up together, can not evenly disperse and separate. In application example 1, the ultrasonic power is 500W, and the time is 2 hours, so that the prepared product is uniformly dispersed molybdenum disulfide flakes. The electrocatalytic performance under this condition is optimal.
Application examples 10 to 11 compare with application example 1, in the electrochemical stripping process, Ni in different nickel salts+Ion and TBA+The ease with which the complex is formed by the ions and DMF. In application example 1, Ni in Nickel chloride+Ion and TBA+The complex formed by ions and DMF is the best. Ni+Ions will dope into the molybdenum disulfide thin layer, resulting in improved electrocatalytic performance.
Comparative example 1
Compared with application example 1, the difference is that bulk molybdenum disulfide is directly used as a catalyst, the test conditions are the same as application example 1, and the overpotential of the obtained bulk molybdenum disulfide material in an alkaline solution is more than-600 mV.
Comparative example 2
Compared with the example 1, the difference is that the electrolyte solution for electrochemically stripping the molybdenum disulfide powder does not contain nickel chloride, and other conditions are the same. And (3) testing under the same condition of the application example 1 to obtain the two-dimensional ultrathin molybdenum disulfide nanosheet with the overpotential of-426 mV in an alkaline solution.
Claims (10)
1. A preparation method of a two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet is characterized by comprising the following steps:
(1) fixing molybdenum disulfide powder on a copper adhesive tape through conductive silver adhesive to serve as a working electrode, and electrochemically stripping in N, N-dimethylformamide electrolyte containing nickel salt and electrolyte to obtain nickel-doped molybdenum disulfide;
(2) filtering and collecting nickel-doped molybdenum disulfide in the electrolyte, washing and drying the nickel-doped molybdenum disulfide, and performing ultrasonic treatment in a dispersion solution;
(3) and carrying out centrifugal separation and freeze drying on the suspension subjected to ultrasonic treatment to obtain the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet.
2. The preparation method of two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets as claimed in claim 1, wherein the preparation method of molybdenum disulfide powder comprises the steps of: and grinding the sulfur powder and the molybdenum powder, sealing the ground sulfur powder and molybdenum powder in a vacuum quartz glass tube, heating the mixture for 2-5 hours at 900-1000 ℃, and cooling to obtain the molybdenum disulfide powder.
3. The method for preparing two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets as recited in claim 1, wherein the nickel salt comprises any one of nickel chloride, nickel acetate, nickel sulfate and nickel nitrate.
4. A method for preparing two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets as recited in claim 1, wherein the electrolyte comprises any one of tetrabutylammonium bromide, tetrapropylammonium bromide, and tetraethylammonium bromide.
5. The preparation method of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet according to claim 1, wherein the negative voltage for electrochemical stripping in step (1) is from-1 to-10V; the time of electrochemical stripping is 20-40 min.
6. The preparation method of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet according to claim 1, wherein the power of ultrasonic treatment in the step (2) is 300-500W, and the time is 1-2 h.
7. The preparation method of two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets as claimed in claim 1, wherein the dispersing solution in step (2) comprises any one of N, N-dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide.
8. The preparation method of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet according to claim 1, wherein the centrifugal separation of the suspension in the step (3) adopts a low-speed centrifugation and high-speed centrifugation method, and specifically comprises the steps of:
(1) low-speed centrifugation: rotating at 2000-4000 rpm for 20-30 min, and collecting supernatant;
(2) high-speed centrifugation: rotating at 8000-12000 rpm, centrifuging for 20-30 min, and collecting precipitate;
(3) washing: and washing the precipitate for 1-3 times by adopting absolute ethyl alcohol and water respectively, wherein the centrifugal rotation speed is 8000-12000 rpm, and the centrifugal time is 20-30 min.
9. The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet prepared by the preparation method according to any one of claims 1 to 8, wherein the average thickness of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet is no greater than 5 nm.
10. The use of two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets as recited in claim 9 in electrochemical hydrogen evolution.
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