CN106099053B - A kind of molybdenum sulfide/selenizing molybdenum composite material and its preparation and application - Google Patents
A kind of molybdenum sulfide/selenizing molybdenum composite material and its preparation and application Download PDFInfo
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- CN106099053B CN106099053B CN201610392008.6A CN201610392008A CN106099053B CN 106099053 B CN106099053 B CN 106099053B CN 201610392008 A CN201610392008 A CN 201610392008A CN 106099053 B CN106099053 B CN 106099053B
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- molybdenum
- selenizing
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- molybdenum sulfide
- sulfide
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 125
- 239000011733 molybdenum Substances 0.000 title claims abstract description 124
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000002604 ultrasonography Methods 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 11
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052961 molybdenite Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VBNIGYNNILMQRE-UHFFFAOYSA-N O.NN.[Se] Chemical compound O.NN.[Se] VBNIGYNNILMQRE-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 41
- 239000002356 single layer Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 241000446313 Lamella Species 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 235000015393 sodium molybdate Nutrition 0.000 description 6
- 239000011684 sodium molybdate Substances 0.000 description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 102000057593 human F8 Human genes 0.000 description 2
- -1 molybdenum sulfide Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229940047431 recombinate Drugs 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/33—
-
- B01J35/396—
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of molybdenum sulfide/selenizing molybdenum composite material and its preparation and application, molybdenum sulfide/selenizing molybdenum composite material is that molybdenum sulfide nanometer sheet surface in situ grows selenizing molybdenum nanometer sheet；Wherein selenizing molybdenum nanometer sheet is with the sheet form vertical-growth that crimps on molybdenum sulfide nanoscale twins.Preparation: single layer or few layer molybdenum sulfide nanometer sheet are prepared by ultrasonic wave added stripping method, then growth in situ lacks layer selenizing molybdenum nanometer sheet on single layer or few layer molybdenum sulfide nanometer sheet by solvent-thermal method.Using: it is widely used in energy fields such as liberation of hydrogen catalyst, lithium ion battery and supercapacitors.The present invention is designed by simple preparation process, is grown few layer selenizing molybdenum nanoscale twins on the single layer or few layer molybdenum sulfide nanoscale twins of ultrasound removing, is obtained the heterojunction structure with multi-stage porous, improve the performances such as its conductive, catalysis.
Description
Technical field
The invention belongs to composite material and its preparation and application field, in particular to a kind of molybdenum sulfide/selenizing molybdenum composite wood
Material and its preparation and application.
Background technique
Recently as the development and application of the dilute equal two-dimension nano materials of graphite, the transition metal with typical layered structure
Chalcogen compound (such as molybdenum sulfide, selenizing molybdenum), be stripped into since its is unique the characteristic of the two-dimentional dilute structure of class graphite with
And they cause the extensive concern of people in the outstanding representation of catalyst, energy stores and field of electronic devices.Stratiform transition
Metal sulfide can use molecular formula MX2It indicates, M represents transition metal element (typically Mo, W etc.), and X represents the member of VI race
Plain (S, Se, Te etc.), the typical lamellar compound being made of the M-X-M of sandwich structure, between layers with Van der Waals force
It combines, therefore block materials are easy to be stripped into the ultrathin nanometer piece of single layer or few layer.Although two sulphur of stratiform transition metal
Compound has similitude in structure, but they show different electronic properties, and two sulphur of stratiform transition metal of body phase
Nature difference between compound and the transition metal dichalcogenide of single layer is also very big, such as molybdenum sulfide nanometer sheet and molybdenum sulfide block phase
Than being changed into direct band-gap semicondictor by indirect band-gap semiconductor, this change makes it that can generate some spies to electricity, magnetic, light etc.
Different reaction.
In the research process to new material, people often adjust the property of existing material as needed, to expand
The performance of corresponding application range and optimization material.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of molybdenum sulfide/selenizing molybdenum composite material and its preparation and answer
Single layer or few layer molybdenum sulfide nanometer sheet are prepared by ultrasonic wave added stripping method with, the present invention, then by solvent-thermal method in single layer or
Growth in situ lacks layer selenizing molybdenum nanometer sheet in few layer molybdenum sulfide nanometer sheet.The present invention makes full use of material molybdenum sulfide interlayer Van der Waals
Power is weaker, it is easily peelable at single layer or few layer nanometer sheet the characteristics of, successfully prepare that chemical property is stable, single layer of large specific surface area
Or few layer molybdenum sulfide nanometer sheet；Molybdenum sulfide prepared by the present invention-selenizing molybdenum composite material has the characteristics that morphology controllable, with stripping
Single layer or few layer molybdenum sulfide nanometer sheet from method preparation are substrate, grow few layer selenizing molybdenum nanometer sheet on its surface, effectively inhibit
The reunion and stacking of selenizing molybdenum nanometer sheet itself, and adjust by constructing semiconductor heterostructure the electronics knot of composite material
Structure improves its electric conductivity, catalytic performance etc. in turn；Molybdenum sulfide prepared by the present invention-selenizing molybdenum composite material is expected to as one
The promising high performance electrode material of kind, has extensively in energy fields such as liberation of hydrogen catalyst, lithium ion battery and supercapacitors
Application.
A kind of molybdenum sulfide/selenizing molybdenum composite material of the invention, the molybdenum sulfide/selenizing molybdenum composite material are received for molybdenum sulfide
Rice piece surface in situ grows selenizing molybdenum nanometer sheet；Wherein selenizing molybdenum nanometer sheet is with the sheet form vertical-growth that crimps in molybdenum sulfide
On nanoscale twins.
A kind of molybdenum sulfide/selenizing molybdenum composite material preparation method of the invention, comprising:
(1) in organic solvent by molybdenite dispersion, ultrasound obtains blackish green dispersion liquid, and centrifugation goes to precipitate, then will be upper
Layer clear liquid is diluted, and obtains the dispersion liquid of molybdenum sulfide nanometer sheet；
(2) selenium powder is added in hydrazine hydrate, stirring obtains selenium-hydrazine hydrate dispersion liquid；Molybdate is dissolved in minor amount of water, is surpassed
Sound sufficiently dissolves, and obtains molybdate dispersion liquid；
(3) dispersion liquid of above-mentioned molybdenum sulfide nanometer sheet, selenium-hydrazine hydrate dispersion liquid, molybdate dispersion liquid are mixed, is carried out molten
Agent thermal response, reaction temperature are 160-220 DEG C, reaction time 10-24h, and obtained black precipitate filters, and washs, dry, are obtained
To molybdenum sulfide/selenizing molybdenum composite material.
Organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- methylpyrrole in the step (1)
Alkanone；It is preferred that N,N-dimethylformamide.
The concentration of molybdenite dispersion in organic solvent is 1-50mg/mL, preferably 5-20mg/mL.
Ultrasonic time is 2-48h, preferably 6-24h in the step (1).
The centrifugation in precipitating is gone in centrifugation in the step (1) are as follows: centrifugal speed 1000-3000rpm, preferably 1500-
2000rpm；Centrifugation time is 2-20min, preferably 5-10min.
The step (1) is diluted to organic solvent and is diluted, and the volume of taken supernatant is 1-6mL, preferably 1-5mL；
Extension rate is 0-10 times, preferably 2-6 times；The total volume for diluting after cure molybdenum dispersion liquid is 10mL.
Dilution is n,N-Dimethylformamide, n,N-dimethylacetamide or N-Methyl pyrrolidone with organic solvent, excellent
Select N,N-dimethylformamide.
In the step (2) selenium-hydrazine hydrate dispersion liquid concentration be 0.5-6mg/mL, preferably 1-4mg/mL, hydrazine hydrate
Volume is 10-30mL.
Sodium molybdate need to be only completely dissolved by the dosage of aqueous solvent in step (2).
Molybdate is ammonium molybdate, sodium molybdate, magnesium molybdate and zinc molybdate etc. in the step (2).
The molar ratio of sodium molybdate and selenium powder is 1:2.
Solvent thermal reaction in the step (3) are as follows: carry out in a kettle, preferably: reaction temperature is 180-200 DEG C, instead
It is 12-18h between seasonable.
Washing is with organic solvent, ethyl alcohol and the repeated multiple times washing of deionized water in step (3).
It is dry in the step (3) are as follows: freeze-drying 12-48h, preferably 24-30h or 60 DEG C vacuum drying 2-12h, preferably
4-8h。
A kind of molybdenum sulfide/selenizing molybdenum composite material application of the invention, molybdenum sulfide/selenizing molybdenum composite material are urged in liberation of hydrogen
Application in agent, lithium ion battery and supercapacitor.
The present invention removes vulcanization molybdenum ore by ultrasonic wave added and obtains single layer or few layer molybdenum sulfide lamella；By selenium powder and molybdic acid
By a step solvent-thermal method, the growth in situ on single layer or few layer molybdenum sulfide lamella lacks layer selenizing molybdenum nanometer sheet and is prepared salt.
The present invention is designed by simple preparation process, raw on the single layer or few layer molybdenum sulfide nanoscale twins of ultrasound removing
Long few layer selenizing molybdenum nanoscale twins, obtain the heterojunction structure with multi-stage porous, improve the performances such as its conductive, catalysis.The molybdenum sulfide-
Selenizing molybdenum composite material has the advantage that (1) has the single layer of unique two-dimensional layered structure or few layer molybdenum sulfide nanometer sheet can
To provide more growth site for selenizing molybdenum, inhibits the reunion and stacking of selenizing molybdenum nanometer sheet, enable selenizing molybdenum nanometer sheet
Expose more active edge sites；Layer selenizing molybdenum nanometer sheet vertical-growth can also be effective on molybdenum sulfide lamella less simultaneously
Inhibit the stacking again of molybdenum sulfide nanoscale twins；(2) in molybdenum sulfide-selenizing molybdenum composite material, by coupling two kinds of level-density parameters
Semiconductor material, molybdenum sulfide and selenizing molybdenum intersection are capable of forming semiconductor heterostructure, can effectively realize separation of charge
Electron-hole is inhibited to recombinate, to improve its electric conductivity and catalytic performance.(3) molybdenum sulfide-selenizing molybdenum composite material can mention
For bigger specific surface area, be conducive to the entrance of electrolyte, the transmission energy of electrode material surface proton and electronics can be obviously improved
Power embodies superior chemical property.Therefore, molybdenum sulfide and the progress of selenizing molybdenum is effectively compound, it is able to achieve good between the two
Synergistic effect, prepare molybdenum sulfide-selenizing molybdenum composite material of electrochemical performance.
Preparation work electrode tests molybdenum sulfide prepared by the present invention-polarization of the selenizing molybdenum composite material in acid condition
Curve, it is specific the preparation method is as follows:
Molybdenum sulfide-selenizing molybdenum composite material prepared by this experiment of 3.0mg is dispersed in 175 μ L dehydrated alcohols and 47 μ L
In Nafion solution, ultrasound obtains uniform dispersion liquid, and taking 2.2 μ L dispersant liquid drops in glassy carbon electrode surface, (glass-carbon electrode is successively
Polished, cleaning obtains clean glass-carbon electrode), molybdenum sulfide-selenizing molybdenum composite material electrode is obtained after natural drying.
Using molybdenum sulfide-selenizing molybdenum composite material electrode as working electrode, saturated calomel electrode is as reference electrode, graphite
Stick is used as to electrode, chooses the 0.5mol/L H of nitrogen saturation2SO4Solution is electrolyte, with the scanning speed p-wire of 2mV/s
Property voltammetric scan curve, as a result as shown in Figure 1.
It is made that the present invention is characterized using transmission electron microscope (TEM), X-ray diffraction (XRD) and electrochemical workstation
Molybdenum sulfide-selenizing molybdenum composite material structure and morphology and electrochemistry obtained, result are as follows:
(1) TEM test result shows: prepared molybdenum sulfide-selenizing molybdenum composite material has unique multilevel structure, In
Edge can be seen the molybdenum sulfide nanoscale twins of few layer or single layer, and selenizing molybdenum nanometer sheet is with the sheet form vertical-growth that crimps in list
On layer or few layer molybdenum sulfide nanoscale twins.In molybdenum sulfide-selenizing molybdenum composite material, there is the single layer or few of unique layer structure
Layer molybdenum sulfide lamella provides more growth sites for selenizing molybdenum, and selenizing molybdenum nanometer sheet is made to be uniformly coated on single layer or few layer
On molybdenum sulfide lamella, inhibit the reunion of selenizing molybdenum itself, so that the selenizing molybdenum nanometer sheet edge with catalytic activity be made to be filled
The exposure divided.
(2) XRD test result show the molybdenum sulfide of removing in 2 θ=14.4,32.7,39.5,49.8,58.3 and 60.2o
Diffraction maximum correspond respectively to (002) of hexagonal crystal system molybdenum sulfide, (100), (103), (105), (110) and (008) crystal face, by force
Diffraction maximum show that the crystallinity of single layer or few layer molybdenum sulfide is fine.Diffraction of the selenizing molybdenum at 2 θ=13.4,32.9 and 56.7 °
Peak corresponds respectively to (002) of hexagonal structure 2H phase selenizing molybdenum, (100) and (110) crystal face.Prepared molybdenum sulfide-selenizing molybdenum
Composite material shows the characteristic peak of molybdenum sulfide and selenizing molybdenum, illustrates that selenizing molybdenum nanometer sheet is successfully carried on molybdenum sulfide lamella
On；But (002) crystal face of molybdenum sulfide nanometer sheet obviously weakens, and shows that selenizing molybdenum nanometer sheet inhibits the heap again of molybdenum sulfide lamella
It is folded.
(3) Electrochemical results show that the molybdenum sulfide of the removing current density at η=355mV just can reach 10mA/
cm2, this may be due to the single layer of removing or the poor catalytic activity of few layer molybdenum sulfide lamella itself.Selenizing molybdenum need to η=
Current density can reach 10mA/cm under 261mV2, this may be since selenizing molybdenum nanometer sheet is self-assembled into nano flower-like structure, cruelly
Reveal less hydrogen evolution activity site.Molybdenum sulfide-selenizing molybdenum composite material shows obvious excellent catalytic activity for hydrogen evolution, η=
Current density can reach 10mA/cm under 201mV2, due to selenizing molybdenum nanometer sheet is evenly coated at single layer or few layer vulcanization molybdenum sheet
On layer, inhibit the reunion of selenizing molybdenum itself, to expose more active edge sites.Furthermore the molybdenum sulfide-that the present invention constructs
Selenizing molybdenum composite material can adjust the electronic structure of both semiconductors, so as to improve its electric conductivity and catalytic activity.
Beneficial effect
(1) preparation process of the present invention is simple, easily operated, is a kind of effective efficiently preparation method；
(2) experimental design is ingenious.
First, this experiment prepares single layer or few layer molybdenum sulfide nanometer sheet by the method that ultrasonic wave added is removed, as life
Long substrate, unique class graphene layer structure provide more growth sites for the growth of selenizing molybdenum nanometer sheet, make selenium
Change molybdenum nanometer sheet to be uniformly coated in single layer or few layer molybdenum sulfide nanometer sheet, inhibits the reunion of selenizing molybdenum itself, to make to have
There is the edge of the selenizing molybdenum nanometer sheet of catalytic activity adequately to be exposed, the electro-chemical activity of material can be significantly improved.
Second, the hydridization of two kinds of Transition-metal dichalcogenides, the sulphur of building are realized by simple solvent thermal process
Change molybdenum-selenizing molybdenum composite material, bigger specific surface area can be provided, the entrance of electrolyte is conducive to, hence it is evident that improves electrode material
The transmittability for expecting surface plasmon and electronics, shows superior chemical property.
Third, in molybdenum sulfide-selenizing molybdenum composite material, by coupling the semiconductor material of two kinds of level-density parameters, in sulphur
Change molybdenum and selenizing molybdenum intersection and construct semiconductor heterostructure, can effectively realize separation of charge to inhibit electron-hole to recombinate,
To improve its electric conductivity and catalytic performance.
Therefore, selenizing molybdenum and molybdenum sulfide progress is effectively compound, it is able to achieve good synergistic effect between the two, so that the two
Advantage be able to sufficiently combine and performance, to prepare molybdenum sulfide-selenizing molybdenum composite material of electrochemical performance.
(3) molybdenum sulfide-selenizing molybdenum composite material prepared by the present invention is expected to as a kind of promising high-performance electrode
Material is widely used in energy fields such as liberation of hydrogen catalyst, lithium ion battery, supercapacitors.
Detailed description of the invention
Fig. 1 is molybdenum sulfide-selenizing molybdenum composite material SEM figure in embodiment 1；
Fig. 2 is molybdenum sulfide in embodiment 1-selenizing molybdenum composite material TEM figure；Wherein a is low magnification；B is put for height
Big multiple；
Fig. 3 is molybdenum sulfide in the present invention-selenizing molybdenum composite material XRD diagram；
Fig. 4 is the linear voltammetric scan curve of molybdenum sulfide in embodiment 1-selenizing molybdenum composite material；
Fig. 5 is the linear voltammetric scan curve of molybdenum sulfide-selenizing molybdenum composite material of different compositions in the present invention.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) 1g molybdenite is added in 100mL n,N-Dimethylformamide, the lower continuous ultrasound in supersonic cleaning machine
12h obtains blackish green dispersion liquid；
(2) single layer obtained in (1) or few layer molybdenum sulfide nanometer sheet dispersion liquid is taken to be centrifuged, centrifugal speed is
1500rpm, centrifugation time 8min remove sediment；
(3) 2.5mL single layer or few layer molybdenum sulfide nanometer sheet dispersion liquid is taken to be carried out with 7.5mL N,N-dimethylformamide dilute
It releases, it is spare；
(4) 25mg selenium powder is dissolved in 10mL hydrazine hydrate, stirring at normal temperature 2h is allowed to evenly dispersed；
(5) 38.3mg sodium molybdate is dissolved in minor amount of water, ultrasound is allowed to sufficiently dissolve；
(6) dispersion liquid prepared in (3) (4) (5) is transferred in hydrothermal synthesis reaction kettle, solvent heat is anti-at 180 DEG C
Answer 12h；
(7) black precipitate being prepared is filtered, and repeatedly more with n,N-Dimethylformamide, ethyl alcohol and deionized water
Secondary cleaning, it is then dry in freeze dryer, molybdenum sulfide-selenizing molybdenum composite material can be obtained, be named as molybdenum sulfide-selenizing molybdenum-
2.Embodiment 2
(1) 1g molybdenite is added in 100mL n,N-Dimethylformamide, the lower continuous ultrasound in supersonic cleaning machine
12h obtains blackish green dispersion liquid；
(2) single layer obtained in (1) or few layer molybdenum sulfide nanometer sheet dispersion liquid is taken to be centrifuged, centrifugal speed is
1500rpm, centrifugation time 8min remove sediment；
(3) 1.25mL single layer or few layer molybdenum sulfide nanometer sheet dispersion liquid is taken to be carried out with 8.75mL N,N-dimethylformamide
Dilution, it is spare；
(4) 25mg selenium powder is dissolved in 10mL hydrazine hydrate, stirring at normal temperature 2h is allowed to evenly dispersed；
(5) 38.3mg sodium molybdate is dissolved in minor amount of water, ultrasound is allowed to sufficiently dissolve；
(6) dispersion liquid prepared in (3) (4) (5) is transferred in hydrothermal synthesis reaction kettle, solvent heat is anti-at 180 DEG C
Answer 12h；
(7) black precipitate being prepared is filtered, and repeatedly more with n,N-Dimethylformamide, ethyl alcohol and deionized water
Secondary cleaning, it is then dry in freeze dryer, molybdenum sulfide-selenizing molybdenum composite material can be obtained, be named as molybdenum sulfide-selenizing molybdenum-
1。
Embodiment 3
(1) 1g molybdenite is added in 100mL n,N-Dimethylformamide, the lower continuous ultrasound in supersonic cleaning machine
12h obtains blackish green dispersion liquid；
(2) single layer obtained in (1) or few layer molybdenum sulfide nanometer sheet dispersion liquid is taken to be centrifuged, centrifugal speed is
1500rpm, centrifugation time 8min remove sediment；
(3) 5mL single layer or few layer molybdenum sulfide nanometer sheet dispersion liquid is taken to be diluted with 5mL n,N-Dimethylformamide, it is standby
With；
(4) 25mg selenium powder is dissolved in 10mL hydrazine hydrate, stirring at normal temperature 2h is allowed to evenly dispersed；
(5) 38.3mg sodium molybdate is dissolved in minor amount of water, ultrasound is allowed to sufficiently dissolve；
(6) dispersion liquid prepared in (3) (4) (5) is transferred in hydrothermal synthesis reaction kettle, solvent heat is anti-at 180 DEG C
Answer 12h；
(7) black precipitate being prepared is filtered, and repeatedly more with n,N-Dimethylformamide, ethyl alcohol and deionized water
Secondary cleaning, it is then dry in freeze dryer, molybdenum sulfide-selenizing molybdenum composite material can be obtained, be named as molybdenum sulfide-selenizing molybdenum-
3。
Claims (10)
1. a kind of molybdenum sulfide/selenizing molybdenum composite material, it is characterised in that: the molybdenum sulfide/selenizing molybdenum composite material is molybdenum sulfide
Nanometer sheet surface in situ grows selenizing molybdenum nanometer sheet；Wherein selenizing molybdenum nanometer sheet is being vulcanized with the sheet form vertical-growth crimped
On molybdenum nanoscale twins.
2. a kind of preparation method of molybdenum sulfide as described in claim 1/selenizing molybdenum composite material, comprising:
(1) in organic solvent by molybdenite dispersion, ultrasound, centrifugation goes to precipitate, and is then diluted supernatant liquor, obtains sulphur
Change the dispersion liquid of molybdenum nanometer sheet；
(2) selenium powder is added in hydrazine hydrate, stirring obtains selenium-hydrazine hydrate dispersion liquid；Molybdate is soluble in water, and ultrasound obtains molybdenum
Hydrochlorate dispersion liquid；
(3) dispersion liquid of above-mentioned molybdenum sulfide nanometer sheet, selenium-hydrazine hydrate dispersion liquid, molybdate dispersion liquid are mixed, carries out solvent heat
Reaction, reaction temperature are 160-220 DEG C, and then reaction time 10-24h is filtered, wash, dry, obtain molybdenum sulfide/selenizing
Molybdenum composite material.
3. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: described
Organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone in step (1)；Molybdenite point
The concentration dissipated in organic solvent is 1-50mg/mL.
4. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: described
Ultrasonic time is 2-48h in step (1).
5. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: step
(1) supernatant liquor is diluted is diluted for organic solvent, and the volume of taken supernatant is 1-6mL, extension rate 0-10
Times, the total volume of dilution after cure molybdenum dispersion liquid is 10mL.
6. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: described
Selenium-hydrazine hydrate dispersion liquid concentration is 0.5-6mg/mL in step (2), and the volume of hydrazine hydrate is 10-30mL.
7. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: described
The molar ratio of molybdate and selenium powder is 1:2 in step (2).
8. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: described
Solvent thermal reaction in step (3) are as follows: carry out in a kettle, reaction temperature is 180-200 DEG C, reaction time 12-18h.
9. a kind of preparation method of molybdenum sulfide/selenizing molybdenum composite material according to claim 2, it is characterised in that: described
It is dry in step (3) are as follows: 12-48h or 60 DEG C of vacuum drying 2-12h of freeze-drying.
10. a kind of application of molybdenum sulfide as described in claim 1/selenizing molybdenum composite material, it is characterised in that: molybdenum sulfide/selenium
Change application of the molybdenum composite material in liberation of hydrogen catalyst, lithium ion battery and supercapacitor.
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| KR102115599B1 (en) * | 2016-12-27 | 2020-05-26 | 주식회사 엘지화학 | Seperator and Lithium sulfur battery comprising the same |
| CN108066778A (en) * | 2017-11-28 | 2018-05-25 | 深圳先进技术研究院 | A kind of preparation method of the photoacoustic imaging molecular probe based on two selenizing molybdenum nanometer sheets |
| CN109321942B (en) * | 2018-11-12 | 2020-10-30 | 安徽师范大学 | Molybdenum selenide nanosheet array/Mo foil composite material, and preparation method and application thereof |
| CN112295866B (en) * | 2019-07-26 | 2022-03-22 | 中国科学院福建物质结构研究所 | Preparation method of all-metal organic framework van der Waals heterojunction layer film, film prepared by preparation method and application of film |
| CN110571416B (en) * | 2019-08-19 | 2021-01-19 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN112002884A (en) * | 2020-08-27 | 2020-11-27 | 扬州大学 | Flower ball shaped MoSe1.48S0.52@ C positive electrode composite material and aluminum ion battery |
| CN112194104B (en) * | 2020-09-16 | 2022-04-26 | 湖北大学 | Preparation method of flower-ball-shaped ZIF-67-molybdenum selenide nano particles |
| CN114289037B (en) * | 2020-09-23 | 2023-07-14 | 天津理工大学 | S-doped Te vacancy type 2H MoTe 2 Preparation method and application of electrocatalyst |
| CN112687760B (en) * | 2020-12-25 | 2022-07-29 | 清远道动新材料科技有限公司 | MoS 2 /MoSe 2 Heterojunction thin film and preparation method and application thereof |
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