CN113617368B - Tungsten disulfide/molybdenum disulfide/graphene composite material with layered structure, and preparation method and application thereof - Google Patents
Tungsten disulfide/molybdenum disulfide/graphene composite material with layered structure, and preparation method and application thereof Download PDFInfo
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- CN113617368B CN113617368B CN202010321901.6A CN202010321901A CN113617368B CN 113617368 B CN113617368 B CN 113617368B CN 202010321901 A CN202010321901 A CN 202010321901A CN 113617368 B CN113617368 B CN 113617368B
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- molybdenum disulfide
- disulfide
- graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 147
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 130
- 239000002131 composite material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000013329 compounding Methods 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000002135 nanosheet Substances 0.000 claims description 49
- 239000011259 mixed solution Substances 0.000 claims description 40
- 239000004094 surface-active agent Substances 0.000 claims description 39
- 238000000227 grinding Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000000703 high-speed centrifugation Methods 0.000 claims description 8
- 238000000464 low-speed centrifugation Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 6
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- SITRHDNMHBAUKP-UHFFFAOYSA-N diammonium trisulphide Chemical compound [NH4+].[NH4+].[S-]S[S-] SITRHDNMHBAUKP-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 108700004121 sarkosyl Proteins 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 235000013878 L-cysteine Nutrition 0.000 claims description 3
- 239000004201 L-cysteine Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- BKRJTJJQPXVRRY-UHFFFAOYSA-M dodecyl-(2-hydroxyethyl)-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCO BKRJTJJQPXVRRY-UHFFFAOYSA-M 0.000 claims description 2
- ACWKAVFAONSRKJ-UHFFFAOYSA-M hexadecyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC=C ACWKAVFAONSRKJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 241000276425 Xiphophorus maculatus Species 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 50
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 37
- 239000008367 deionised water Substances 0.000 description 35
- 229910021641 deionized water Inorganic materials 0.000 description 35
- 239000010410 layer Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 27
- -1 transition metal sulfide Chemical class 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 229910052723 transition metal Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a tungsten disulfide/molybdenum disulfide/graphene composite material, which has a layered structure; and compounding the flaky tungsten disulfide, flaky molybdenum disulfide and graphene sheets to form a layered structure. According to the tungsten disulfide composite material provided by the invention, tungsten disulfide, molybdenum disulfide and graphene are compounded through electrostatic adsorption, so that the tungsten disulfide composite material has a specific layered structure, more active sites and higher active surface area can be provided, the catalytic activity of tungsten disulfide is greatly improved, the HER performance is improved, and excellent catalytic hydrogen evolution performance is shown. The preparation method is simple, mild in condition, easy to operate and low in cost, and can better promote the commercial application of the tungsten disulfide composite catalyst. The invention not only provides an excellent catalyst for the hydrogen evolution field, but also provides a new idea for preparing the synthesis of the composite two-dimensional catalyst.
Description
Technical Field
The invention belongs to the technical field of tungsten disulfide HER catalyst materials, relates to a tungsten disulfide/molybdenum disulfide/graphene composite material, a preparation method and application thereof, and particularly relates to a tungsten disulfide/molybdenum disulfide/graphene composite material with a layered structure, and a preparation method and application thereof.
Background
Hydrogen energy is an ideal, clean and efficient secondary energy source. Electrocatalytic, photoelectrocatalytic decomposition of water is one of the important sources of hydrogen, while high performance electrocatalysts are the core of electrolyzed and photoelectrodecomposed water. At present, noble metal Pt and alloys thereof are mainly adopted as the HER catalyst of the widely applied water electrolysis catalyst, but the high cost and resource scarcity of the Pt-based HER catalyst severely restrict the wide application of the Pt-based HER catalyst as the HER catalyst. The search for inexpensive, highly active, acid stable hydrogen evolution catalysts has been a current research hotspot.
The chemical formula of the two-dimensional transition metal sulfide is MX 2 M refers to transition metal elements (e.g., molybdenum, tungsten, niobium, rhenium, titanium), and X refers to chalcogenides (e.g., sulfur, selenium, tellurium). The strong spin-orbit coupling effect and structural diversity of the material endows the material with a plurality of novel physical properties, such as WTE in a few layers 1Td phase 2 Quantum spin hall effect was observed in the minority layer 2H phase MoS 2 With NbSe 2 And the like, is observed. These findings make MX2 materials a hotspot for current aggregate physics and materials science research. Also, typically, the single layer transition metal sulfide exhibits a sandwich structure of X-M-X. The van der waals forces between the layers are weak, yet there are very strong covalent bonds in the plane. Bulk transition metal sulfides can be exfoliated like graphene into single or multi-layered nanoplatelets. The band gap of many two-dimensional transition metal sulfides is in the range of 1 to 2eV, with the band gap increasing as the number of layers decreases. Some two-dimensional transition metal sulfides, such as chalcogenides of molybdenum and tungsten, have an indirect band gap when the material is in a multilayer structure, and the band structure is converted to a direct band gap when the material is exfoliated into a monolayer. The single-layer two-dimensional transition metal sulfide has a direct band gap energy band structure, can improve light emission efficiency, and brings a trigger for preparing high-performance photoelectric devices.
Of more note are transition metal disulfides, e.g. MoS 2 、WS 2 、MoSe 2 And WSe 2 Hydrogen Evolution Reactions (HER) have been used by many scientists. The transition metal disulfide has unique catalytic action and high earth content, which will be a simple and low cost way to produce hydrogen. Although WS 2 Is a stable high activity catalyst for HER, but further improvements are needed, particularly WS as prepared by conventional methods 2 Catalytic performance is not ideal, and many researchers have improved it by constructing special structures and compounding with other materials. However, the traditional method for preparing the composite catalyst mainly comprises a stepwise solvothermal method, a CVD method, a high-temperature calcination method and other methods and processes, and the composite catalyst is preparedThe method is high, complex and tedious.
Therefore, how to find a simple composite mode and a more suitable tungsten disulfide composite catalyst can change WS by using a simple method 2 Is suitable for industrialized popularization and application, and becomes one of the problems to be solved urgently for a plurality of first-line researchers and scientific enterprises.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a tungsten disulfide/molybdenum disulfide/graphene composite material, and a preparation method and application thereof, in particular to a tungsten disulfide/molybdenum disulfide/graphene composite material with a layered structure. The tungsten disulfide composite material provided by the invention has a specific layered structure, and greatly improves the capability of the catalytic activity of tungsten disulfide, so that the HER performance is improved, and the preparation method is simple, mild in condition, easy to operate and low in cost, and can better promote the commercialized application of the tungsten disulfide composite catalyst.
The invention provides a tungsten disulfide/molybdenum disulfide/graphene composite material, which has a layered structure;
and compounding the flaky tungsten disulfide, flaky molybdenum disulfide and graphene sheets to form a layered structure.
Preferably, the flaky molybdenum disulfide and the flaky tungsten disulfide are compounded on the graphene sheet;
the flaky molybdenum disulfide comprises molybdenum disulfide micro-nano tablets;
the flaky tungsten disulfide comprises a tungsten disulfide micro-nano tablet;
the graphene sheets comprise graphene micro-nano sheets;
the mass ratio of the graphene sheet to the flaky tungsten disulfide is (0.5-2): 10;
the mass ratio of the flaky molybdenum disulfide to the flaky tungsten disulfide is (0.5-2): 1, a step of;
the sheet diameter of the graphene sheet is 5-15 mu m.
Preferably, the thickness of the graphene sheet is 1-10 nm;
the sheet diameter of the flaky molybdenum disulfide is 5-10 mu m;
the thickness of the flaky molybdenum disulfide is 5-12 nm;
the sheet diameter of the sheet tungsten disulfide is 2-7 mu m;
the thickness of the flaky tungsten disulfide is 1-12 nm;
the compounding includes layering.
Preferably, the complexing is complexing by electrostatic adsorption;
the flaky molybdenum disulfide and the flaky tungsten disulfide are respectively compounded on the graphene sheet layer and/or the flaky molybdenum disulfide and the flaky tungsten disulfide are laminated and compounded on the graphene sheet layer;
The flaky molybdenum disulfide is compounded between the flaky tungsten disulfide and the graphene sheets;
the composite material has a wrinkled microscopic morphology;
the folds include mountain folds and/or wave folds;
and gaps are formed among the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheets.
The invention provides a preparation method of a tungsten disulfide/molybdenum disulfide/graphene composite material, which comprises the following steps:
1) Dispersing molybdenum disulfide powder, a first surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a molybdenum disulfide micro-nano tablet;
dispersing and mixing the expanded graphite, the second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain graphene micro-nano sheets;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A;
2) Dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, a sulfur source, a third surfactant and water again to obtain a mixed solution B;
3) And (3) mixing the mixed solution B and the mixed solution A again, regulating the pH value, and reacting to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
Preferably, the first surfactant comprises one or more of sodium dodecyl benzene sulfonate, sodium N-lauroyl sarcosinate, sodium dodecyl sulfate, sodium fatty alcohol ether sulfate and alcohol acyl phosphate;
the mass ratio of the molybdenum disulfide powder to the first surfactant is (1-5): 100;
the mass ratio of the molybdenum disulfide powder to the water is (0.5-3): 100;
the second surfactant comprises one or more of ethylenediamine, octadecyltrimethylammonium chloride, polyetherimide, hexadecyldimethylallylammonium chloride, tetradecyldimethylbenzyl ammonium chloride, dodecyl dimethylhydroxyethyl ammonium chloride and dodecyl trimethyl ammonium chloride;
the mass ratio of the expanded graphite to the second surfactant is (1-5): 100;
the mass ratio of the expanded graphite to the water is (0.5-3): 100;
the dispersing and dispersing mixing modes comprise ultrasonic stirring dispersing;
the centrifugation process specifically comprises the following steps: centrifuging at a low speed to obtain an upper layer liquid, and centrifuging at a high speed to obtain a lower layer liquid;
the centrifugation is followed by a drying step.
Preferably, the ultrasonic frequency of the ultrasonic stirring dispersion is 20-40 KHz;
the rotation speed of ultrasonic stirring and dispersing is 300-500 rpm;
The ultrasonic stirring and dispersing time is 120-360 min;
the rotating speed of the low-speed centrifugation is 500-1000 rpm;
the low-speed centrifugation time is 3-5 min;
the rotating speed of the high-speed centrifugation is 3000-5000 rpm;
the high-speed centrifugation time is 5-10 min;
the drying is vacuum drying.
Preferably, the drying temperature is 40-80 ℃;
the drying time is 6-24 hours;
the grinding time is 30-60 min;
the grinding rotating speed is 1000-1500 rpm;
the fineness of the graphene micro-nano sheet and the molybdenum disulfide micro-nano sheet is 10-30 mu m;
the mol ratio of the tungsten hexachloride to the ammonium tungstate is (0.2-1): 1, a step of;
the mass ratio of the molybdenum disulfide micro-nano sheet to the graphene micro-nano sheet is 10 (0.5-2);
the molar ratio of the total number of moles of tungsten hexachloride and ammonium tungstate to the sulfur source is 1: (2.5-3);
the sulfur source includes one or more of sulfur, thiourea, thiol, ammonium trisulfide, thioacetamide and L-cysteine.
Preferably, the third surfactant comprises one or more of cetyltrimethylammonium bromide, octadecene, polyvinylpyrrolidone and F127;
the mass ratio of the molybdenum disulfide micro-nano tablet to the third surfactant is (1-10): 100;
The redispersion mode is ultrasonic dispersion;
the redispersion time is 10-30 min;
the mode of remixing is slow addition;
the pH value is 5-7;
the temperature of the reaction is 160-240 ℃;
the reaction time is 12-24 h.
The invention also provides the application of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes in the aspect of hydrogen evolution reaction.
The invention provides a tungsten disulfide/molybdenum disulfide/graphene composite material, which has a layered structure; sheet tungsten disulfide, sheet molybdenum disulfide and graphene sheet are compounded to form a layer junctionConstructing a structure. Compared with the prior art, the invention aims at the prior WS 2 Further improvements in catalytic performance are required and WS prepared by conventional processes 2 Catalytic performance is not ideal and is enhanced by constructing a special structure and compounding with other materials. But also has the problems of complex and tedious method and process and high cost.
The tungsten disulfide composite material with a special structure is creatively designed, and is compounded with tungsten disulfide, molybdenum disulfide and graphene through electrostatic adsorption, has a specific layered structure, can provide more active sites and higher active surface area, greatly improves the catalytic activity capacity of the tungsten disulfide, improves the HER performance, shows excellent catalytic hydrogen evolution performance, and effectively solves the defect that only the boundary of the tungsten disulfide has catalytic activity and the surface of the tungsten disulfide has no catalytic activity.
Compared with the traditional stepwise solvothermal method, CVD method and high-temperature calcination method, the preparation method provided by the invention has the advantages of simplicity, mild condition, easiness in operation and low cost, and can better promote the commercialization application of the tungsten disulfide composite catalyst. The invention not only provides an excellent catalyst for the hydrogen evolution field, solves the problems that the traditional hydrogen evolution catalyst is mainly noble metal such as Pt and the like, has high cost and prevents the large-scale application and the commercial development of the catalyst, but also provides a new thought for the synthesis of the preparation of the composite two-dimensional catalyst.
Experimental results show that the tungsten disulfide/molybdenum disulfide/graphene composite catalyst prepared by the method has a smaller Tafel slope (104 mV/dec) and shows excellent hydrogen evolution catalytic performance.
Drawings
FIG. 1 is a flow chart diagram of a specific preparation process of a tungsten disulfide/molybdenum disulfide/graphene composite material provided by an embodiment of the invention;
FIG. 2 is a TEM transmission electron microscope image of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 1 of the present invention;
FIG. 3 is an HR-TEM high-power transmission electron microscope image of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 2 of the present invention;
FIG. 4 is a TEM transmission electron microscope image of a tungsten disulfide micro-nano sheet prepared in example 3 of the present invention;
FIG. 5 is a graph showing polarization curves of a catalyst prepared from the tungsten disulfide composite prepared in example 1 and a catalyst prepared from the tungsten disulfide prepared in example 3 of the present invention;
FIG. 6 is a Tafil plot of a catalyst prepared from a tungsten disulfide composite prepared in example 1 and a catalyst prepared from tungsten disulfide prepared in example 3 of the present invention;
FIG. 7 is a graph of electrochemical impedance of a catalyst prepared from the tungsten disulfide composite prepared in example 1 and a catalyst prepared from tungsten disulfide prepared in example 3 of the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs analytically pure or conventional purity used in the field of lithium-sulfur battery separator preparation.
The invention provides a tungsten disulfide/molybdenum disulfide/graphene composite material, which has a layered structure;
And compounding the flaky tungsten disulfide, flaky molybdenum disulfide and graphene sheets to form a layered structure.
The invention has no special limitation on the specific structural relation of the composite in principle, and the technical personnel in the field can select and adjust according to the actual application situation, the product requirement and the quality requirement, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving the HER performance, and the flaky molybdenum disulfide and the flaky tungsten disulfide are preferably compounded on the graphene sheet; more specifically, the flaky molybdenum disulfide and the flaky tungsten disulfide are preferably respectively compounded on the graphene sheets and/or the flaky molybdenum disulfide and the flaky tungsten disulfide are laminated and compounded on the graphene sheets, more preferably the flaky molybdenum disulfide and the flaky tungsten disulfide are laminated and compounded on the graphene sheets, and even more specifically the flaky molybdenum disulfide is preferably compounded between the flaky tungsten disulfide and the graphene sheets.
According to the invention, different surfactants are used for modifying molybdenum disulfide and graphene, so that the surfaces of the molybdenum disulfide sheet and the graphene sheet are respectively provided with negative charges and positive charges, when the modified molybdenum disulfide sheet and the modified graphene sheet are mixed, the graphene sheet can be loaded with molybdenum disulfide, after a tungsten source is added, tungsten positive ions can be loaded on the other surface of the molybdenum disulfide through the action of charges, (because the positive charges on the surface of the graphene can repel tungsten positive ions, most of the tungsten positive ions cannot be loaded on the surface of the graphene sheet), and a tungsten disulfide nano sheet is formed through hydrothermal reaction, so that the tungsten disulfide/molybdenum disulfide/graphene composite material is obtained.
The invention is not particularly limited in principle to the specific mode of the compounding, and a person skilled in the art can select and adjust the mode according to actual application conditions, product requirements and quality requirements.
The invention is not particularly limited in principle to the specific kind of the composite, and a person skilled in the art can select and adjust the composite according to practical application situations, product requirements and quality requirements.
The invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance. The sheet diameter of the sheet-like molybdenum disulfide is preferably 5 to 10. Mu.m, more preferably 6 to 9. Mu.m, and still more preferably 7 to 8. Mu.m. The thickness of the flaky molybdenum disulfide is preferably 5 to 12nm, more preferably 6 to 11nm, still more preferably 7 to 10nm, and still more preferably 8 to 9nm.
The specific parameters of the flaky tungsten disulfide are not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art. The sheet diameter of the sheet-like tungsten disulfide is preferably 2 to 7. Mu.m, more preferably 3 to 6. Mu.m, and still more preferably 4 to 5. Mu.m. The thickness of the flaky tungsten disulfide is preferably 1 to 12nm, more preferably 3 to 10nm, and still more preferably 5 to 8nm.
The specific parameters of the graphene sheet are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements. The graphene sheet preferably has a sheet diameter of 5 to 15. Mu.m, more preferably 7 to 13. Mu.m, and still more preferably 9 to 11. Mu.m. The thickness of the graphene sheet is preferably 1 to 10nm, more preferably 3 to 8nm, and still more preferably 5 to 6nm.
The invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby further improving HER performance, and the mass ratio of the graphene sheets to the flaky tungsten disulfide is preferably (0.5-2): 10, more preferably (0.8 to 1.7): 10, more preferably (1.1 to 1.4): 10.
the invention has no special limitation on the proportion of the flaky molybdenum disulfide in the composite material in principle, and the proportion can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the mass ratio of the flaky molybdenum disulfide to the flaky tungsten disulfide is preferably (0.5-2): 1, more preferably (0.8 to 1.7): 1, more preferably (1.1 to 1.4): 1.
the morphology of the composite material is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, so as to further improve HER performance, and the composite material preferably has a microscopic morphology of folds, and the folds preferably comprise mountain folds and/or wave folds, and more preferably comprise mountain folds and wave folds. The flaky tungsten disulfide, flaky molybdenum disulfide and graphene sheets preferably have gaps.
The invention also provides a preparation method of the tungsten disulfide/molybdenum disulfide/graphene composite material, which comprises the following steps:
1) Dispersing molybdenum disulfide powder, a first surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a molybdenum disulfide micro-nano tablet;
dispersing and mixing the expanded graphite, the second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain graphene micro-nano sheets;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A;
2) Dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, a sulfur source, a third surfactant and water again to obtain a mixed solution B;
3) And (3) mixing the mixed solution B and the mixed solution A again, regulating the pH value, and reacting to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
Firstly, dispersing molybdenum disulfide powder, a first surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain molybdenum disulfide micro-nano tablets;
dispersing and mixing the expanded graphite, the second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain graphene micro-nano sheets;
After tungsten hexachloride, ammonium tungstate and water are mixed, a mixed solution A is obtained.
The present invention is not particularly limited in principle, and the type of the first surfactant may be selected and adjusted by those skilled in the art according to practical application, product requirements and quality requirements, and the present invention provides more active sites and higher active surface area for better ensuring specific structure and morphology of the composite material, so as to improve HER performance, and the first surfactant preferably includes one or more of sodium dodecyl benzene sulfonate, sodium N-lauroyl sarcosinate, sodium dodecyl sulfate, sodium fatty alcohol ether sulfate and alcohol acyl phosphate, and more preferably includes sodium dodecyl benzene sulfonate, sodium N-lauroyl sarcosinate, sodium dodecyl sulfate, sodium fatty alcohol ether sulfate or alcohol acyl phosphate.
The proportion of the first surfactant is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, so as to further improve HER performance, wherein the mass ratio of the molybdenum disulfide powder to the first surfactant is preferably (1-5): 100, more preferably (1.5 to 4.5): 100, more preferably (2 to 4): 100, more preferably (2.5 to 3.5): 100.
The invention is in principle not particularly limited to the proportion of the water, and a person skilled in the art can select and adjust the proportion according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the mass ratio of the molybdenum disulfide powder to the water is preferably (0.5-3): 100, more preferably (1 to 2.5): 100, more preferably (1.5 to 2): 100.
the second surfactant is not particularly limited in kind, and can be selected and adjusted by those skilled in the art according to practical application, product requirements and quality requirements, so that the specific structure and morphology of the composite material are better ensured, more active sites and higher active surface area are provided, and further HER performance is improved.
The proportion of the second surfactant is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, so as to further improve HER performance, and the mass ratio of the expanded graphite to the second surfactant is preferably (1-5): 100, more preferably (1.5 to 4.5): 100, more preferably (2 to 4): 100, more preferably (2.5 to 3.5): 100.
the invention is in principle not particularly limited to the proportion of the water, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the mass ratio of the expanded graphite to the water is preferably (0.5-3): 100, more preferably (1 to 2.5): 100, more preferably (1.5 to 2): 100.
the dispersion and the dispersion mixing mode are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, so that HER performance is improved, and the dispersion mode preferably comprises ultrasonic stirring dispersion. The dispersing and mixing mode of the invention preferably comprises ultrasonic stirring and dispersing.
The invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the ultrasonic frequency of ultrasonic stirring dispersion is preferably 20-40 KHz, more preferably 22-38 KHz, more preferably 25-35 KHz, more preferably 28-32 KHz. The rotation speed of the ultrasonic agitation dispersion is preferably 300 to 500rpm, more preferably 330 to 480rpm, still more preferably 350 to 450rpm, and still more preferably 380 to 430rpm. The ultrasonic agitation and dispersion time is preferably 120 to 360 minutes, more preferably 150 to 330 minutes, still more preferably 180 to 300 minutes, and still more preferably 210 to 270 minutes.
The invention is not particularly limited in principle to the specific process and parameters of the centrifugation, and a person skilled in the art can select and adjust the centrifugation according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface areas for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the centrifugation process is specifically as follows: centrifuging at low speed to obtain supernatant, and centrifuging at high speed to obtain lower supernatant. The rotational speed of the low-speed centrifugation is preferably 500 to 1000rpm, more preferably 600 to 900rpm, and still more preferably 700 to 800rpm. The low-speed centrifugation time is preferably 3 to 5 minutes, more preferably 3.3 to 4.7 minutes, still more preferably 3.6 to 4.4 minutes, and still more preferably 3.9 to 4.1 minutes. The rotational speed of the high-speed centrifugation is preferably 3000 to 5000rpm, more preferably 3300 to 4700rpm, still more preferably 3600 to 4400rpm, still more preferably 3900 to 4100rpm. The time for the high-speed centrifugation is preferably 5 to 10 minutes, more preferably 6 to 9 minutes, and still more preferably 7 to 8 minutes.
The invention provides more active sites and higher active surface area for the complete and refined whole preparation process, better ensures the specific structure and morphology of the composite material, further improves HER performance, and preferably comprises a drying step after centrifugation, wherein the drying is preferably vacuum drying. Specifically, the drying temperature is preferably 40 to 80 ℃, more preferably 45 to 75 ℃, still more preferably 50 to 70 ℃, still more preferably 55 to 65 ℃. The drying time is preferably 6 to 24 hours, more preferably 9 to 21 hours, and still more preferably 12 to 18 hours.
The specific process and parameters of the grinding are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the grinding time is preferably 30-60 min, more preferably 35-55 min, and even more preferably 40-50 min, so that the specific structure and morphology of the composite material are better ensured, more active sites and higher active surface area are provided, and further HER performance is improved. The rotational speed of the grinding is preferably 1000 to 1500rpm, more preferably 1100 to 1400rpm, and still more preferably 1200 to 1300rpm.
The fineness of the grinded graphene micro-nano sheet is not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, so that the specific structure and morphology of the composite material are better ensured, more active sites and higher active surface area are provided, further HER performance is improved, the fineness of the graphene micro-nano sheet is preferably 10-30 mu m, more preferably 12-28 mu m, more preferably 15-25 mu m, and more preferably 17-22 mu m.
The fineness of the ground molybdenum disulfide micro-nano sheet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, so that the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the fineness of the molybdenum disulfide micro-nano sheet is preferably 10-30 mu m, more preferably 12-28 mu m, more preferably 15-25 mu m, and more preferably 17-22 mu m.
The molar ratio of the tungsten hexachloride to the ammonium tungstate is not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, so that the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the molar ratio of the tungsten hexachloride to the ammonium tungstate is preferably (0.2-1): 1, more preferably (0.3 to 0.9): 1, more preferably (0.4 to 0.8): 1, more preferably (0.5 to 0.7): 1.
and then, dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, a sulfur source, a third surfactant and water again to obtain a mixed solution B.
The sulfur source is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring specific structure and morphology of the composite material, so as to further improve HER performance, wherein the sulfur source preferably comprises one or more of sulfur, thiourea, thiol, ammonium trisulfide, thioacetamide and L-cysteine, and more preferably comprises sulfur, thiourea, thiol, ammonium trisulfide, thioacetamide or L-cysteine.
The invention is not particularly limited in principle to the addition amount of the sulfur source, and a person skilled in the art can select and adjust the sulfur source according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the molar ratio of the total mole number of tungsten hexachloride and ammonium tungstate to the sulfur source is preferably 1: (2.5 to 3), more preferably 1: (2.6 to 2.9), more preferably 1: (2.7-9).
The proportion of the molybdenum disulfide micro-nano sheet to the graphene micro-nano sheet is not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, so that the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, further improves HER performance, and the mass ratio of the molybdenum disulfide micro-nano sheet to the graphene micro-nano sheet is preferably 10 (0.5-2), more preferably 10: (0.8 to 1.7), more preferably 10: (0.8-1.7).
The present invention is not particularly limited in principle, and the type of the third surfactant may be selected and adjusted by those skilled in the art according to practical application, product requirements and quality requirements, and the present invention provides more active sites and higher active surface area for better ensuring specific structure and morphology of the composite material, so as to improve HER performance, and the third surfactant preferably includes one or more of cetyltrimethylammonium bromide, octadecene, polyvinylpyrrolidone and F127, and more preferably is cetyltrimethylammonium bromide, octadecene, polyvinylpyrrolidone or F127.
The mass ratio of the molybdenum disulfide micro-nano tablet to the third surfactant is not particularly limited in principle, and can be selected and adjusted according to practical application conditions, product requirements and quality requirements by a person skilled in the art, so that the invention provides more active sites and higher active surface areas for better ensuring the specific structure and morphology of the composite material, further improves HER performance, and the mass ratio of the molybdenum disulfide micro-nano tablet to the third surfactant is preferably (1-10): 100, more preferably (3 to 8): 100, more preferably (5 to 6): 100.
The redispersion process and parameters are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, so that the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, and further improves HER performance, the redispersion mode is preferably ultrasonic dispersion, more particularly, the redispersion time is preferably 10-30 min, more preferably 13-27 min, more preferably 16-24 min, and more preferably 19-21 min.
Finally, mixing the mixed solution B and the mixed solution A obtained in the steps again, regulating the pH value, and reacting to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
The pH value is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, so that the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving HER performance, and the pH value is preferably 5-7, more preferably 5.3-6.7, more preferably 5.6-6.4, and even more preferably 5.9-6.1.
The invention is not particularly limited in principle to the parameters of the reaction, and can be selected and adjusted by a person skilled in the art according to practical application conditions, product requirements and quality requirements, and the invention provides more active sites and higher active surface area for better ensuring the specific structure and morphology of the composite material, thereby improving the HER performance, and the temperature of the reaction is preferably 160-240 ℃, more preferably 170-230 ℃, more preferably 180-220 ℃, and more preferably 190-210 ℃. More specifically, the reaction time is preferably 12 to 24 hours, more preferably 14 to 22 hours, and still more preferably 16 to 20 hours.
The preparation method of the tungsten disulfide/molybdenum disulfide/graphene composite material is a complete and refined integral preparation process, better ensures the specific structure and morphology of the composite material, provides more active sites and higher active surface area, and further improves HER performance, and specifically comprises the following steps:
adding a certain amount of molybdenum disulfide powder and a first surfactant into deionized water, and performing ultrasonic dispersion to form a dispersion; then, taking an upper layer liquid through low-speed centrifugation, taking a lower layer through high-speed centrifugation, and finally, drying and grinding in vacuum to form a molybdenum disulfide micro-nano sheet;
Adding a certain amount of expanded graphite and a second surfactant into deionized water, and performing ultrasonic dispersion to form a dispersion liquid; then, taking an upper layer liquid through low-speed centrifugation, taking a lower layer through high-speed centrifugation, and finally, drying and grinding in vacuum to form graphene micro-nano sheets;
adding certain mass of tungsten hexachloride and ammonium tungstate into deionized water, and magnetically stirring to form a mixed solution A;
adding a molybdenum disulfide micro-nano sheet, a graphene micro-nano sheet, a sulfur source and a third surfactant into water, and performing ultrasonic dispersion to form a mixed solution B;
slowly adding the mixed solution B into the solution A, regulating the pH value, transferring into a stainless steel reaction kettle with polytetrafluoroethylene lining, heating for reacting for a period of time, naturally cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for three times, finally drying in vacuum, and grinding to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
Referring to fig. 1, fig. 1 is a schematic flow chart of a specific preparation process of a tungsten disulfide/molybdenum disulfide/graphene composite material provided by an embodiment of the present invention.
The invention also provides the application of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes in the aspect of hydrogen evolution reaction.
The invention provides a tungsten disulfide/molybdenum disulfide/graphene composite material with a layered structure, and a preparation method and application thereof. According to the tungsten disulfide composite material with the special layered structure, provided by the invention, tungsten disulfide, molybdenum disulfide and graphene are compounded through electrostatic adsorption, and the tungsten disulfide/molybdenum disulfide/graphene ordered laminated composite material has a specific layered structure, so that more active sites and higher active surface area can be provided, the catalytic activity of tungsten disulfide is greatly improved, the HER performance is improved, the excellent catalytic hydrogen evolution performance is shown, and the defect that only the boundary of single transition metal tungsten disulfide has catalytic activity and the surface of the single transition metal tungsten disulfide has no catalytic activity is effectively solved.
Compared with the traditional stepwise solvothermal method, CVD method and high-temperature calcination method, the preparation method provided by the invention has the advantages of simplicity, mild condition, easiness in operation and low cost, and can better promote the commercialization application of the tungsten disulfide composite catalyst. The invention not only provides an excellent catalyst for the hydrogen evolution field, solves the problems that the traditional hydrogen evolution catalyst is mainly noble metal such as Pt and the like, has high cost and prevents the large-scale application and the commercial development of the catalyst, but also provides a new thought for the synthesis of the preparation of the composite two-dimensional catalyst.
Experimental results show that the tungsten disulfide/molybdenum disulfide/graphene composite catalyst prepared by the method has a smaller Tafel slope (104 mV/dec) and shows excellent hydrogen evolution catalytic performance.
For further explanation of the present invention, the tungsten disulfide/molybdenum disulfide/graphene composite material, the preparation method and the application thereof are described in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation processes are given only for further explanation of the features and advantages of the present invention, and not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Adding a certain amount of molybdenum disulfide powder and sodium dodecyl sulfate into deionized water, wherein the mass ratio of the molybdenum disulfide powder to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the mixture in vacuum at 60 ℃ overnight to form the molybdenum disulfide micro-nano tablets.
Adding a certain amount of expanded graphite and octadecyl trimethyl ammonium chloride into deionized water, wherein the mass ratio of the expanded graphite to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the graphene micro-nano sheets overnight in vacuum drying at 60 ℃ to form the graphene micro-nano sheets.
1.1896g of tungsten hexachloride and 0.8517g of ammonium tungstate are added into 36ml of deionized water, and the mixture is magnetically stirred for 10min to form a mixed A solution;
0.7439g of molybdenum disulfide micro-nano tablets, 0.0744g of graphene micro-nano tablets, 2.2836g of thiourea and polyvinylpyrrolidone with a certain mass are added into 36ml of deionized water, and ultrasonic dispersion is carried out for 30min to form a mixed solution B;
slowly adding the mixed solution B into the solution A, regulating the pH value to 5-7, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 200 ℃, naturally cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for three times, finally drying in vacuum, and grinding to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
The tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 1 of the invention is characterized.
Referring to fig. 2, fig. 2 is a TEM transmission electron microscope image of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 1 of the present invention.
As can be seen from FIG. 2 in combination with the following FIG. 4, the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by the invention has an obvious laminated structure, layered tungsten disulfide micro-nano sheets, layered molybdenum disulfide micro-nano sheets and graphene sheets are orderly laminated together, the three layered materials have a micron-scale sheet diameter and a nanometer-scale thickness, and the whole composite material has a similar corrugation microscopic morphology as a mountain or wave. Further based on common sense judgment, gaps are needed to be formed among the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheets, and more gaps with irregular shapes are needed.
Performance detection is carried out on the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 1 of the invention. For specific detection results, see comparative detection results in example 3, which follows.
Example 2
Adding a certain amount of molybdenum disulfide powder and sodium dodecyl sulfate into deionized water, wherein the mass ratio of the molybdenum disulfide powder to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the mixture in vacuum at 60 ℃ overnight to form the molybdenum disulfide micro-nano tablets.
Adding a certain amount of expanded graphite and octadecyl trimethyl ammonium chloride into deionized water, wherein the mass ratio of the expanded graphite to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the graphene micro-nano sheets overnight in vacuum drying at 60 ℃ to form the graphene micro-nano sheets.
1.1896g of tungsten hexachloride and 0.8517g of ammonium tungstate are added into 36ml of deionized water, and the mixture is magnetically stirred for 10min to form a mixed A solution;
0.7439g of molybdenum disulfide micro-nano tablets, 0.0744g of graphene micro-nano tablets, 2.2836g of thiourea and polyvinylpyrrolidone with a certain mass are added into 36ml of deionized water, and ultrasonic dispersion is carried out for 30min to form a mixed solution B;
slowly adding the mixed solution B into the solution A, regulating the pH value to 5-7, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 24 hours, naturally cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for three times, finally drying in vacuum, and grinding to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
The tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 2 of the invention is characterized.
Referring to fig. 3, fig. 3 is an HR-TEM high power transmission electron microscope image of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 2 of the present invention.
As can be seen from fig. 3, the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by the method has an obvious laminated structure, the layered tungsten disulfide micro-nano sheets, the layered molybdenum disulfide micro-nano sheets and the graphene sheets are orderly laminated together, the three layered materials have a micron-sized sheet diameter and a nanometer-sized thickness, and the whole composite material has a similar corrugation microscopic morphology as a mountain or a wave. Further based on common sense judgment, gaps are needed to be formed among the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheets, and more gaps with irregular shapes are needed.
Example 3
1.1896g of tungsten hexachloride and 0.8517g of ammonium tungstate are added into 36ml of deionized water, and the mixture is magnetically stirred for 10min to form a mixed A solution;
2.2836g of thiourea and polyvinylpyrrolidone with a certain mass are added into 36ml of deionized water, and ultrasonic dispersion is carried out for 30min to form a mixed solution B;
slowly adding the mixed solution B into the solution A, transferring the mixed solution A into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 220 ℃, naturally cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for three times, finally drying in vacuum, and grinding to obtain the tungsten disulfide material.
The tungsten disulfide material prepared in example 3 of the present invention was characterized.
Referring to fig. 4, fig. 4 is a TEM transmission electron microscope of the tungsten disulfide micro-nano sheet prepared in example 3 of the present invention.
Comparative performance detection was performed on the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 1 of the present invention and the tungsten disulfide material prepared in example 3.
Preparation of electrodes
The prepared composite material catalyst is coated on a glassy carbon electrode to serve as an electrocatalytic hydrogen production electrode and is used for electrocatalytic hydrogen evolution.
The rotary disk glassy carbon electrode is used as a working electrode, and the surface of the rotary disk glassy carbon electrode is polished and pre-cleaned by using an alumina solution and then naturally dried in the sun. Mixing the composite material catalyst with an alcohol water solution (V/V=7:3), uniformly dispersing by ultrasonic (ultrasonic is required to be uniform in each use), taking 14.5 mu L of mixed solution by using a digital electric pipettor, coating the mixed solution on a rotary disk glassy carbon electrode, naturally airing in a clean environment, and carrying out electrochemical test.
Electrochemical test method
The electrochemical performance of the catalyst is measured by the electrochemical workstation. The electrochemical workstation is connected with the H-type electrolytic tank through a three-electrode system, the electrolyte is 1M KOH aqueous solution, meanwhile, an external computer device timely transmits an electric signal to a computer, and the performance index of the material is obtained by analyzing specific data.
Referring to fig. 5, fig. 5 is a polarization graph of a catalyst prepared from the tungsten disulfide composite prepared in example 1 and a catalyst prepared from the tungsten disulfide prepared in example 3 according to the present invention.
As can be seen from FIG. 5, the tungsten disulfide composite catalyst prepared by the invention has the best hydrogen evolution catalytic activity.
Referring to fig. 6, fig. 6 is a tafel plot of the catalyst prepared from the tungsten disulfide composite prepared in example 1 and the catalyst prepared from tungsten disulfide prepared in example 3 of the present invention.
As can be seen from FIG. 6, the Tafel slope was used as a benchmark for evaluating the intrinsic properties of electrocatalysts, the catalyst prepared in example 1 and the Tafel slope (104 and 207 mV/dec) of the pure tungsten disulfide catalyst samples. The faster the current density of the catalyst prepared in example 1 increases with increasing overpotential, the faster hydrogen evolution reaction rate can be easily achieved, and the smaller tafel slope indicates that the catalyst prepared in example 1 has superior catalytic performance.
Comparative electrochemical performance detection was performed on the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 1 of the present invention and the tungsten disulfide material prepared in example 3.
Referring to fig. 7, fig. 7 is a graph showing electrochemical resistance of a catalyst prepared from the tungsten disulfide composite material prepared in example 1 and a catalyst prepared from the tungsten disulfide prepared in example 3 according to the present invention.
As can be seen from fig. 7, the radius of semicircle of the ac impedance curve of the composite catalyst prepared by the present invention is smaller than that of the ac impedance curve of the pure tungsten disulfide catalyst, which indicates that the catalyst prepared in example 1 has good electron transfer rate.
Example 4
Adding a certain amount of molybdenum disulfide powder and sodium dodecyl sulfate into deionized water, wherein the mass ratio of the molybdenum disulfide powder to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the mixture in vacuum at 60 ℃ overnight to form the molybdenum disulfide micro-nano tablets.
Adding a certain amount of expanded graphite and octadecyl trimethyl ammonium chloride into deionized water, wherein the mass ratio of the expanded graphite to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the graphene micro-nano sheets overnight in vacuum drying at 60 ℃ to form the graphene micro-nano sheets.
1.1896g of tungsten hexachloride and 0.8517g of ammonium tungstate are added into 36ml of deionized water, and the mixture is magnetically stirred for 10min to form a mixed A solution;
0.7439g of molybdenum disulfide micro-nano tablets, 0.0372g of graphene micro-nano tablets, 2.2836g of thiourea and polyvinylpyrrolidone with a certain mass are added into 36ml of deionized water, and ultrasonic dispersion is carried out for 30min, so as to form a mixed solution B;
slowly adding the mixed solution B into the solution A, regulating the pH value to 5-7, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 200 ℃, naturally cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for three times, finally drying in vacuum, and grinding to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
The tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 4 of the invention is characterized.
The results show that the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 4 has a similar layered morphology of orderly laminated composite.
Example 5
Adding a certain amount of molybdenum disulfide powder and sodium dodecyl sulfate into deionized water, wherein the mass ratio of the molybdenum disulfide powder to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the mixture in vacuum at 60 ℃ overnight to form the molybdenum disulfide micro-nano tablets.
Adding a certain amount of expanded graphite and octadecyl trimethyl ammonium chloride into deionized water, wherein the mass ratio of the expanded graphite to the deionized water is 1:100, forming a mixed solution, and performing ultrasonic dispersion for 120min to form a dispersion solution; centrifuging at low speed of 500rmp/min for 5min, collecting upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting lower layer solution, and washing; and then drying and grinding the graphene micro-nano sheets overnight in vacuum drying at 60 ℃ to form the graphene micro-nano sheets.
1.1896g of tungsten hexachloride and 0.8517g of ammonium tungstate are added into 36ml of deionized water, and the mixture is magnetically stirred for 10min to form a mixed A solution;
0.7439g of molybdenum disulfide micro-nano tablets, 0.1498g of graphene micro-nano tablets, 2.2836g of thiourea and polyvinylpyrrolidone with a certain mass are added into 36ml of deionized water, and ultrasonic dispersion is carried out for 30min, so as to form a mixed solution B;
slowly adding the mixed solution B into the solution A, regulating the pH value to 5-7, transferring into a stainless steel reaction kettle with polytetrafluoroethylene lining, reacting at 160 ℃ for 24 hours, naturally cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for three times, finally drying in vacuum, and grinding to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material
The tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 5 of the invention is characterized.
The results show that the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 5 has a similar layered morphology of orderly laminated composite.
The tungsten disulfide/molybdenum disulfide/graphene composite material with a layered structure, and the preparation method and application thereof provided by the invention are described in detail, and specific examples are used herein to illustrate the principles and embodiments of the invention, and the description of the examples is only for aiding in understanding the method and core concept of the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system, and implementing any combined method. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The tungsten disulfide/molybdenum disulfide/graphene composite material is characterized by having a layered structure;
the flaky tungsten disulfide, flaky molybdenum disulfide and the graphene sheets are compounded to form a layered structure;
the flaky molybdenum disulfide and the flaky tungsten disulfide are compounded on the graphene sheet;
the flaky molybdenum disulfide comprises molybdenum disulfide micro-nano tablets;
the flaky tungsten disulfide comprises a tungsten disulfide micro-nano tablet;
the flaky molybdenum disulfide and the flaky tungsten disulfide are laminated and compounded on the graphene sheet;
the flaky molybdenum disulfide is compounded between the flaky tungsten disulfide and the graphene sheets;
the sheet diameter of the graphene sheet is 5-15 mu m;
the thickness of the graphene sheet is 1-10 nm;
the sheet diameter of the flaky molybdenum disulfide is 5-10 mu m;
the thickness of the flaky molybdenum disulfide is 5-12 nm;
the sheet diameter of the sheet tungsten disulfide is 2-7 mu m;
the thickness of the flaky tungsten disulfide is 1-12 nm;
the compounding includes layering;
the mass ratio of the graphene sheet to the sheet tungsten disulfide is (0.5-2): 10;
the mass ratio of the flaky molybdenum disulfide to the flaky tungsten disulfide is (0.5-2): 1.
2. the composite material of claim 1, wherein the platy molybdenum disulfide and platy tungsten disulfide are composited on the graphene platelet;
The graphene sheets include graphene micro-nano sheets.
3. The composite material of claim 1, wherein the compounding is compounding by electrostatic adsorption.
4. The composite of claim 1, wherein the composite has a wrinkled microscopic morphology;
the folds include mountain folds and/or wave folds;
and gaps are formed among the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheets.
5. A method for preparing the tungsten disulfide/molybdenum disulfide/graphene composite material according to any one of claims 1 to 4, comprising the following steps:
1) Dispersing molybdenum disulfide powder, a first surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a molybdenum disulfide micro-nano tablet;
dispersing and mixing the expanded graphite, the second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain graphene micro-nano sheets;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A;
2) Dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, a sulfur source, a third surfactant and water again to obtain a mixed solution B;
3) And (3) mixing the mixed solution B and the mixed solution A again, regulating the pH value, and reacting to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
6. The method of preparing according to claim 5, wherein the first surfactant comprises one or more of sodium dodecyl benzene sulfonate, sodium N-lauroyl sarcosinate, sodium dodecyl sulfate, sodium fatty alcohol ether sulfate, and alcohol acyl phosphate;
the mass ratio of the molybdenum disulfide powder to the first surfactant is (1-5): 100;
the mass ratio of the molybdenum disulfide powder to the water is (0.5-3): 100;
the second surfactant comprises one or more of ethylenediamine, octadecyltrimethylammonium chloride, polyetherimide, hexadecyldimethylallylammonium chloride, tetradecyldimethylbenzyl ammonium chloride, dodecyl dimethylhydroxyethyl ammonium chloride and dodecyl trimethyl ammonium chloride;
the mass ratio of the expanded graphite to the second surfactant is (1-5): 100;
the mass ratio of the expanded graphite to the water is (0.5-3): 100;
the dispersing and dispersing mixing modes comprise ultrasonic stirring dispersing;
the centrifugation process specifically comprises the following steps: centrifuging at a low speed to obtain an upper layer liquid, and centrifuging at a high speed to obtain a lower layer liquid;
The centrifugation is followed by a drying step.
7. The preparation method of claim 6, wherein the ultrasonic frequency of ultrasonic stirring dispersion is 20-40 khz;
the rotating speed of ultrasonic stirring and dispersing is 300-500 rpm;
the ultrasonic stirring and dispersing time is 120-360 min;
the rotating speed of the low-speed centrifugation is 500-1000 rpm;
the low-speed centrifugation time is 3-5 min;
the rotating speed of the high-speed centrifugation is 3000-5000 rpm;
the high-speed centrifugation time is 5-10 min;
the drying is vacuum drying.
8. The method according to claim 6, wherein the drying temperature is 40-80 ℃;
the drying time is 6-24 hours;
the grinding time is 30-60 min;
the grinding rotating speed is 1000-1500 rpm;
the fineness of the graphene micro-nano sheet and the molybdenum disulfide micro-nano sheet is 10-30 mu m;
the molar ratio of the tungsten hexachloride to the ammonium tungstate is (0.2-1): 1, a step of;
the mass ratio of the molybdenum disulfide micro-nano sheet to the graphene micro-nano sheet is 10 (0.5-2);
the molar ratio of the total number of moles of tungsten hexachloride and ammonium tungstate to the sulfur source is 1: (2.5-3);
the sulfur source includes one or more of sulfur, thiourea, thiol, ammonium trisulfide, thioacetamide and L-cysteine.
9. The method of preparing according to claim 5, wherein the third surfactant comprises one or more of cetyltrimethylammonium bromide, octadecene, polyvinylpyrrolidone and F127;
the mass ratio of the molybdenum disulfide micro-nano tablet to the third surfactant is (1-10): 100;
the redispersion mode is ultrasonic dispersion;
the redispersion time is 10-30 min;
the mode of remixing is slow addition;
the pH value is 5-7;
the temperature of the reaction is 160-240 ℃;
the reaction time is 12-24 hours.
10. The use of the tungsten disulfide/molybdenum disulfide/graphene composite material according to any one of claims 1 to 4 or the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by the preparation method according to any one of claims 5 to 9 in hydrogen evolution reaction.
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