CN113151857B - Two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets and preparation method and application thereof - Google Patents
Two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets and preparation method and application thereof Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 125
- 239000002135 nanosheet Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- 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 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 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 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 238000000703 high-speed centrifugation Methods 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
- 239000000203 mixture Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 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
- 238000000926 separation method 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- 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 19
- 150000002500 ions Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002244 precipitate 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
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal chalcogenide compound Chemical class 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
- 230000003197 catalytic effect Effects 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
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010408 sweeping Methods 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
- 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
- 238000009825 accumulation Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 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
- 238000011031 large-scale manufacturing process 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 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
- 238000013021 overheating Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene 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
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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 relates to the technical field of nano material preparation, in particular to a two-dimensional ultrathin nickel doped molybdenum disulfide nano sheet 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 carrying out electrochemical 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 (3) centrifugally separating and freeze-drying the suspension after ultrasonic treatment to obtain the nickel-doped molybdenum disulfide nanosheets. The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared by the method have the advantages of ultrathin lamellar structure, uniform thickness and good crystallinity, are used for the electrolytic water cathode material, and have 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 nano sheet, and a preparation method and application thereof.
Background
Hydrogen is very abundant on earth and can have very high energy density, and is an ideal choice for replacing traditional fossil fuels in the future. Compared with other hydrogen energy preparation technologies, such as biological hydrogen production and chemical fuel hydrogen production, the electrolytic water hydrogen production has the characteristics of high efficiency and cleanness.
At present, noble metal platinum-based catalysts are the most efficient hydrogen-producing electrocatalysts, but the scarcity of the noble metal platinum-based catalysts and the high 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 features that are not present in their blocky counterparts. Molybdenum sulfide is a typical two-dimensional transition metal chalcogenide compound that exhibits excellent electrochemical hydrogen evolution properties when its size is reduced to nano-scale and exfoliated into single-layer nanoplatelets due to its two-dimensional structure and unique physicochemical properties. Therefore, it is very interesting to develop an effective method to exfoliate the molybdenum disulfide sheet without compromising its structural integrity, thereby preserving its specific properties.
At present, the method for preparing the two-dimensional ultrathin molybdenum disulfide nanosheets comprises a lithium ion intercalation method, a liquid phase ultrasonic stripping method, a mechanical stripping method and the like.
For example, the patent publication No. CN103833081A discloses that a single-layer to several-layer molybdenum disulfide nano-sheet is prepared by lithium ion intercalation molybdenum disulfide powder and then hydrolysis ultrasonic treatment, and the prepared molybdenum disulfide nano-sheet has better quality. However, the lithium ion intercalation treatment in the preparation process is not suitable for industrial mass production because of the need of an anhydrous and anaerobic environment.
The liquid phase ultrasonic stripping method is to make solvent molecules intercalate bulk materials through ultrasonic process, thereby realizing stripping of the materials into flake form. According to the method, polyaniline conductive polymers and molybdenum disulfide powder are uniformly mixed in water or an organic solvent, and then two-dimensional molybdenum disulfide nano-sheets are obtained through physical modes such as ultrasonic and vibration. The liquid phase ultrasonic stripping method has simple steps and operation, but the product quality is not easy to control, and the problems of long treatment time and low efficiency exist, and the method 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 great operation difficulty, the methods are not suitable for industrialized mass production.
Therefore, the preparation method of the cathode hydrogen evolution material is simple to operate, low in cost and high in product quality, is suitable for large-scale industrial production and application, and has great significance in meeting the requirement of large-scale water electrolysis hydrogen production in the future, further popularizing hydrogen energy in daily life and solving the energy and environmental problems.
Disclosure of Invention
The invention aims to overcome the defects of the two-dimensional material stripping method in the prior art, is not suitable for mass production and the problem that the prepared catalyst has an unsatisfactory effect, and provides the preparation method of the two-dimensional ultrathin nickel doped molybdenum disulfide nanosheets which has low production cost and high product catalytic efficiency and is suitable for mass production, and has a certain significance for further developing hydrogen energy and solving the energy environment problem.
In order to achieve the above purpose, the invention adopts the following technical scheme:
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 as a working electrode, and carrying out electrochemical 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, drying, and performing ultrasonic treatment in a dispersion solution;
(3) And centrifugally separating and freeze-drying the suspension after ultrasonic treatment to obtain the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets.
The invention adopts an electrochemical method to strip molybdenum disulfide powder, and simultaneously, nickel element is doped into the product, and before voltage is applied, the molybdenum disulfide powder is a bulk block, and is of a structure with stacked sheets. When negative voltage is applied to the working electrode, the electrolyte and Ni in the electrolyte + And N, N-Dimethylformamide (DMF) solution forms a complex to permeate between layers of bulk molybdenum disulfide, and slowly overcomes Van der Waals force between the molybdenum disulfide layers, so that the molybdenum disulfide layers are separated from the layers, and meanwhile, ni + The method has the advantages that the method is low in cost, high in product quality, simple and efficient, and suitable for large-scale production.
The molybdenum disulfide powder can be purchased from the market, and can also be prepared by the following steps: grinding sulfur powder and molybdenum powder, sealing in a vacuum quartz glass tube, heating the mixture for 2-5 h at 900-1000 ℃, and cooling to obtain the molybdenum disulfide powder. The temperature rise rate is usually 1-10 ℃/min. The nickel doped molybdenum disulfide nanosheets obtained by adopting the self-made molybdenum disulfide powder prepared by the method have better application effect because the commercial molybdenum disulfide powder product has unstable performance.
The nickel salt is soluble salt and comprises any one of nickel chloride, nickel acetate, nickel sulfate and nickel nitrate. Preferably, the nickel salt is nickel chloride, and the inventor finds that the nickel chloride has more uniform thickness and better electrocatalytic effect compared with molybdenum disulfide nanosheets prepared from other nickel salts through experiments.
The electrolyte comprises any one of tetrabutylammonium bromide, tetrapropylammonium bromide and tetraethylammonium bromide. Electrolyte in electrolyte solutionThe complex formed by the medium and nickel ions and DMF solution enters between molybdenum disulfide sheets (the interlayer spacing is 0.62 nm) to promote stripping of molybdenum disulfide, so that the electrolyte with proper molecular size is selected to play a key role in stripping effect, wherein TBA in tetrabutylammonium bromide + Ion size of 0.89nm, TPA in tetrapropylammonium bromide + The ion size was 0.67nm, TEA in tetraethylammonium bromide + The ion size was 0.56nm. Preferably, the electrolyte is tetrabutylammonium bromide.
The magnitude of the applied negative voltage and the time of the maintained applied voltage are the most critical roles in preparing high quality nickel doped molybdenum disulfide flakes. The negative voltage of the electrochemical stripping in the step (1) is-1 to-10V; the electrochemical stripping time is 20-40 min. The molybdenum disulfide stripping quality is not high due to the fact that the negative voltage is applied excessively, the obtained nickel-doped molybdenum disulfide sheet is thicker, stripping efficiency is low due to the fact that the negative voltage is applied excessively, and the yield of the obtained nickel-doped molybdenum disulfide sheet is low. Therefore, proper applied voltage is required to be selected, and the nickel-doped molybdenum disulfide sheet with high quality and high yield can be obtained in the stripping process. Preferably, the electrochemical stripping time is 25 to 35 minutes, most preferably, the electrochemical stripping time is 30 minutes.
In the step (1), the counter electrode adopts a foil, the general production counter electrode and the working electrode are placed in parallel, the placing distance is 1-3 cm, and the stripping rate and the balance of the thermal effect of the molybdenum disulfide can be controlled.
In the step (2), the pore diameter of the filter membrane is not more than 0.2 mu m, so that molybdenum disulfide particles can be removed well, and the peeled molybdenum disulfide slices are ensured to be in the ultrasonic solution.
The power of ultrasonic treatment in the step (2) is 300-500W, and the time is 1-2 h. In the electrochemical stripping process, TBA + Ions and TBA + The complex formed by the ions and DMF can enter the interlayer of molybdenum disulfide together to break the Van der Waals force between the layer and the interlayer. Subsequent ultrasonic treatment can open the molybdenum disulfide sheet more, and finally, the uniformly dispersed molybdenum disulfide sheet can be obtained. Wherein, the greater ultrasonic power and time can lead to the crushing degree of the molybdenum disulfide flake, the ultrasonic power and theThe shorter time can result in the accumulation of molybdenum disulfide flakes that are not evenly dispersed. The quality of the obtained nano-sheet is optimal under the treatment of ultrasonic power of 500W and time of 2 hours. Wherein each time the ultrasound is operated for a period of time, for example for 1s, for 0.5s, to prevent overheating of the sonication apparatus.
In the step (2), the dispersion solution is selected from organic solvents which can be mutually dissolved with water, including N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like, and the dispersion solution can influence the stripping efficiency and the quality of products, wherein the N, N-dimethylformamide organic solvent is used as a stripping solution, and the prepared molybdenum disulfide flake has the best quality.
The centrifugal separation of the suspension in the step (3) adopts a method of low-speed centrifugation and high-speed centrifugation, and specifically comprises the following steps:
(1) Low speed centrifugation: the rotating speed is 2000-4000 rpm, the centrifugation time is 20-30 min, and the supernatant is taken;
(2) High speed centrifugation: the rotating speed is 8000-12000 rpm, the centrifugation time is 20-30 min, and the sediment is taken;
(3) Washing: the sediment is respectively washed by absolute ethyl alcohol and water for 1 to 3 times, the centrifugal speed is 8000 to 12000rpm, and the centrifugal time is 20 to 30 minutes.
The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets with higher quality can be obtained by using high-low speed step-by-step centrifugal treatment. In the low-speed centrifugation process, part of molybdenum disulfide nano-sheets with larger thickness, larger particles or uneven layering are deposited on the lower layer, so that supernatant liquid is taken in the low-speed centrifugation process, and the supernatant liquid is mainly molybdenum disulfide nano-sheets with smaller thickness and uniformity; in the high-speed centrifugation process, trace impurities and molybdenum disulfide powder which is not flaky are separated out through rapid rotation centrifugation, so that the molybdenum disulfide nanosheets with uniform thickness and average thickness not more than 5nm are obtained.
The invention also provides the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared by the preparation method, which are characterized in that the average thickness of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets is not more than 5nm. The voltage and time of the electrochemical stripping process, the ultrasonic time in the later stage, the centrifugal process and the like are comprehensively controlled in the preparation process, so that the finally obtained nickel doped molybdenum disulfide nano-sheet has uniform thickness, the average thickness is not more than 3.5nm, and the ultrathin nano-sheet with the layered structure has good crystallization performance and excellent electrochemical hydrogen evolution performance in application.
The invention also provides application of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets in electrochemical hydrogen evolution. The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets are used for the electrolytic water cathode material, and have excellent electrochemical hydrogen evolution performance and good stability in alkaline solution. When the current density is 10 mA.cm -2 When the two-dimensional ultrathin nickel doped molybdenum disulfide nanosheet material is used, the two-dimensional ultrathin nickel doped molybdenum disulfide nanosheet material shows excellent overpotential-145 mV in a three-electrode alkaline solution test, is kept at a constant voltage for 7200s in a stability test, has small current change of a catalyst, and 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, wherein the molybdenum disulfide powder is stripped by adopting an electrochemical method, meanwhile, nickel element is doped into a product, and the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet is prepared by adopting a one-step method.
(2) The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared by the method have the advantages of being ultrathin, layered, uniform in thickness and good in crystallinity, have the average thickness of not more than 5nm, are used for the electrolytic water cathode material, and have 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 nano-sheet prepared in example 1, and the inset is a selected area diffraction image SAED.
Fig. 2 is an AFM image of a two-dimensional ultrathin 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 nanoplatelets prepared in example 1.
Fig. 4 is a polarization graph of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared in example 1 in an electrolytic water hydrogen evolution reaction.
FIG. 5 is a graph showing the current change with time under constant voltage of two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
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 stoichiometric ratio, fully grinding, and sealing the mixture in a vacuum quartz glass tube;
(2) Heating the mixture from room temperature by using a tube furnace, wherein the heating temperature is 950 ℃, the holding time is 5h, the heating rate is 5 ℃/min, and naturally cooling after heating is completed, so as to obtain molybdenum disulfide powder.
2. Preparation of electrolyte
(1) About 50mL of N, N-dimethylformamide was weighed, 1g of tetrabutylammonium bromide and 0.6g of nickel chloride hexahydrate were weighed, dissolved and stirred with N, N-dimethylformamide, and the volume was set in a 100mL volumetric flask to obtain an electrolyte.
3. Electrochemical stripping molybdenum disulfide powder
(1) Connecting molybdenum disulfide powder to a copper adhesive tape by using a conductive silver adhesive to form an electrode, wherein the electrode is used as a working electrode, a platinum sheet with the length of 1.5cm multiplied by 1.5cm is used as a counter electrode, an N, N-dimethylformamide solution containing tetrabutylammonium bromide and nickel chloride is used as electrolyte, and the counter electrode and the working electrode are placed into the electrolyte at a distance of 2 cm;
(2) Applying a voltage of-10V to the working electrode and keeping for 30min;
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 polytetrafluoroethylene filter and rinsed multiple times with ultrapure water, the flakes 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 was 500W and the ultrasonic time was 2h, wherein the ultrasonic operation was suspended for 1s and for 0.5s.
6. Step-wise centrifugation
(1) Centrifuging the dispersion liquid containing the nickel-doped molybdenum disulfide slices after the completion of the ultrasonic treatment, setting the low-speed centrifugal rotation speed to 4000rpm, centrifuging for 30min, and taking supernatant;
(2) Centrifuging the supernatant at high speed, setting the rotation speed of the high-speed centrifugation to 10000rmp, and taking precipitate, wherein the centrifugation time is 30min;
(3) Washing the precipitate with ultrapure water and absolute ethanol for 3 times respectively, centrifuging at 10000rpm for 30min, and collecting precipitate.
7. Freeze-drying treatment
And (3) performing freeze drying treatment on the precipitate obtained in the step (6) to obtain the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets. The result is shown in fig. 1, wherein the inset is a selected area diffraction image SAED, and the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets are in an ultrathin layered structure. The AFM of the molybdenum disulfide nanosheets is shown in FIG. 2, and the average thickness of the two-dimensional ultrathin nickel doped molybdenum disulfide nanosheets can be measured to be about 3.5nm. As shown in figure 3, the X-ray diffraction XRD of the nickel-doped molybdenum disulfide nanosheets shows that the electrochemical stripping method does not change the composition of molybdenum disulfide.
Examples 2 to 3
According to the preparation process of the embodiment 1, the voltage in stripping in the step 3 is changed to-5V and 15V respectively, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different stripping voltage conditions are obtained.
Examples 4 to 5
According to the preparation process of the embodiment 1, the time in stripping in the step 3 is respectively changed into 10min and 45min, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different stripping time conditions 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 into 300W and 600W, and the rest steps are unchanged, so that the ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different ultrasonic power conditions are obtained.
Examples 8 to 9
According to the preparation process of the embodiment 1, the ultrasonic time in the step 5 is respectively changed into 1 hour and 3 hours, 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, nickel salts in the step 2 are respectively changed into nickel sulfate and nickel nitrate, 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) Using a three-electrode system, wherein the working electrode is the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet of the embodiment 1, the counter electrode is a carbon rod, the reference electrode is a saturated silver/silver chloride electrode, and the electrolyte is 1M potassium hydroxide solution;
(2) CV activation: the electrochemical workstation of Shanghai Chenhua CHI 660E was used, and nitrogen was introduced into the electrolyte for 30min before testing. And a CV program is adopted, the test interval is 0-0.8V vs. RHE, the sweeping speed is 50mV/s, 30 circles are circulated, and the electrode reaches a stable state.
(3) Linear Sweep Voltammetry (LSV) test: after CV activation, the switching program is an LSV program, the test interval is 0-0.8V vs. RHE, and the sweeping speed is 5mV/s. The polarization curve is shown in FIG. 4, and the overpotential of the catalyst in the alkaline solution was observed to be-145 mV.
(4) Stability test: after CV activation, the switching procedure was i-t, the voltage was set to-0.3V (vs. RHE), and the time was set to 7200s. The current change curve with time at constant voltage is shown in fig. 5, and the current change of the catalyst is not large, thus proving good stability.
The embodiment illustrates that the obtained two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets are used as an electrolytic water cathode material, and have excellent electrochemical performance and good stability in alkaline solution. The hydrogen reduction properties of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different stripping conditions in alkaline solution are shown in table 1.
Table 1 performance tables of catalysts in application examples 1 to 11
As can be seen from Table 1, application examples 2 to 11 are two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared under different conditions, and the current density in alkaline solution reaches 10mA.cm -2 The overpotential at this time was larger than that of application example 1. Application examples 2 to 3 compared with application example 1, the negative voltage applied during electrochemical stripping driven TBA + Ions enter the interlayer of molybdenum disulfide, and the TBA is caused by too small voltage application + The number of ion-embedded molybdenum disulfide layers is small, the interval between molybdenum disulfide layers is not opened, and the prepared product is thicker and has lower electrocatalytic performance; excessive voltage application results in TBA + The number of the ion embedded molybdenum disulfide layers is too large, the damage to the molybdenum disulfide layers is serious, the quality of the obtained product is low, and the electrocatalytic performance is low.
Application examples 4 to 5 compared with application example 1, the time applied during electrochemical stripping was the lead TBA + The ion quantity enters molybdenum disulfideIs an interlayer key factor of (a). TBA (Tunnel boring A) + The excessive ion quantity can cause serious damage to the molybdenum disulfide thin layer, the prepared product has low quality and weaker electrocatalytic performance; TBA (Tunnel boring A) + The Van der Waals force between the molybdenum disulfide layers cannot be broken due to the fact that the number of ions is small, the prepared product is thicker, and the same electrocatalytic performance is not high.
Compared with application examples 6-9 and application example 1, the product obtained by electrochemical stripping has great influence on the dispersion degree of the molybdenum disulfide thin layer in the ultrasonic process, wherein the ultrasonic power and time are large, the molybdenum disulfide thin layer is broken, the ultrasonic power and time are small, the molybdenum disulfide thin layer is piled up together, and the molybdenum disulfide thin layer cannot be uniformly dispersed. In application example 1, the ultrasonic power is 500W, and the product prepared for 2 hours is a uniformly dispersed molybdenum disulfide sheet. The electrocatalytic properties under this condition are optimal.
Application examples 10 to 11 are compared with application example 1, ni in different nickel salts during electrochemical stripping + Ion and TBA + The ease with which ions and DMF form complexes is related. In application example 1, ni in Nickel chloride + Ion and TBA + The complex formed by ions and DMF is optimal. Ni (Ni) + Ions will dope into the molybdenum disulfide thin layer, resulting in improved electrocatalytic properties.
Comparative example 1
Compared with application example 1, the difference is only that bulk molybdenum disulfide is directly used as a catalyst, the test conditions are the same as those of application example 1, and the overpotential of the obtained bulk molybdenum disulfide material in alkaline solution is more than-600 mV.
Comparative example 2
The difference compared with example 1 is that the electrolyte solution for electrochemically stripping molybdenum disulfide powder does not contain nickel chloride, and the other conditions are the same. The test was performed under the same conditions as in application example 1, and the overpotential of the obtained two-dimensional ultrathin molybdenum disulfide nanosheets in the alkaline solution was-426 mV.
Claims (8)
1. The preparation method of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets is characterized by comprising the following steps of:
(1) Fixing molybdenum disulfide powder on a copper adhesive tape through conductive silver adhesive as a working electrode, and carrying out electrochemical stripping in N, N-dimethylformamide electrolyte containing nickel salt and electrolyte to obtain nickel-doped molybdenum disulfide; the negative voltage of electrochemical stripping is-1 to-10V; the electrochemical stripping time is 20-40 min;
(2) Filtering and collecting nickel-doped molybdenum disulfide in the electrolyte, washing, drying, and performing ultrasonic treatment in a dispersion solution;
(3) Centrifugally separating and freeze-drying the suspension after ultrasonic treatment to obtain the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets;
the electrolyte comprises any one of tetrabutylammonium bromide, tetrapropylammonium bromide and tetraethylammonium bromide;
the centrifugal separation of the suspension in the step (3) adopts a method of low-speed centrifugation and then high-speed centrifugation, wherein the low-speed centrifugation speed is 2000-4000 rpm, and the high-speed centrifugation speed is 8000-12000 rpm.
2. The method for preparing the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets according to claim 1, wherein the method for preparing the molybdenum disulfide powder comprises the following steps: grinding sulfur powder and molybdenum powder, sealing in a vacuum quartz glass tube, heating the mixture for 2-5 h at 900-1000 ℃, and cooling to obtain the molybdenum disulfide powder.
3. The method for preparing the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets according to claim 1, wherein the nickel salt comprises any one of nickel chloride, nickel acetate, nickel sulfate and nickel nitrate.
4. The method for preparing the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets according to claim 1, wherein the power of ultrasonic treatment in the step (2) is 300-500W, and the time is 1-2 h.
5. The method for preparing the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets according to claim 1, wherein the dispersion solution in the step (2) comprises any one of N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide.
6. The method for preparing the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets according to claim 1, wherein the centrifugal separation of the suspension in the step (3) specifically comprises the steps of:
(1) Low speed centrifugation: the rotating speed is 2000-4000 rpm, the centrifugation time is 20-30 min, and the supernatant is taken;
(2) High speed centrifugation: the rotating speed is 8000-12000 rpm, the centrifugation time is 20-30 min, and the sediment is taken;
(3) Washing: the sediment is respectively washed by absolute ethyl alcohol and water for 1 to 3 times, the centrifugal speed is 8000 to 12000rpm, and the centrifugal time is 20 to 30 minutes.
7. The two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets prepared by the preparation method according to any one of claims 1 to 6, wherein the average thickness of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets is not more than 5nm.
8. The use of the two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheets in electrochemical hydrogen evolution according to claim 7.
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