CN113617368A - 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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- CN113617368A CN113617368A CN202010321901.6A CN202010321901A CN113617368A CN 113617368 A CN113617368 A CN 113617368A CN 202010321901 A CN202010321901 A CN 202010321901A CN 113617368 A CN113617368 A CN 113617368A
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- molybdenum disulfide
- disulfide
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 156
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000013329 compounding Methods 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- 239000002135 nanosheet Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 239000011259 mixed solution Substances 0.000 claims description 50
- 239000004094 surface-active agent Substances 0.000 claims description 40
- 238000000227 grinding Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 28
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 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
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000703 high-speed centrifugation Methods 0.000 claims description 7
- 238000000464 low-speed centrifugation Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 5
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000004697 Polyetherimide Substances 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
- 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 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
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- BKRJTJJQPXVRRY-UHFFFAOYSA-M dodecyl-(2-hydroxyethyl)-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCO BKRJTJJQPXVRRY-UHFFFAOYSA-M 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 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 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 108700004121 sarkosyl Proteins 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000013878 L-cysteine Nutrition 0.000 claims description 2
- 239000004201 L-cysteine Substances 0.000 claims description 2
- SITRHDNMHBAUKP-UHFFFAOYSA-N diammonium trisulphide Chemical compound [NH4+].[NH4+].[S-]S[S-] SITRHDNMHBAUKP-UHFFFAOYSA-N 0.000 claims description 2
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 238000012876 topography Methods 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 47
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 35
- 229910021641 deionized water Inorganic materials 0.000 description 35
- 239000000243 solution Substances 0.000 description 33
- 239000010410 layer Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 16
- -1 transition metal sulfide Chemical class 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 229910052723 transition metal Inorganic materials 0.000 description 11
- 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
- 230000005540 biological transmission Effects 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005229 chemical vapour deposition Methods 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
- 238000011160 research Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 230000005355 Hall effect Effects 0.000 description 1
- 229910020039 NbSe2 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 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
- 229910003090 WSe2 Inorganic materials 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
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 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
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 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
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002105 nanoparticle 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
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 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
- 239000007858 starting material 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
Images
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, the flaky molybdenum disulfide and the graphene sheet 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, and the tungsten disulfide composite material has a specific layered structure, can provide more active sites and a higher active surface area, and greatly improves the capacity of tungsten disulfide catalytic activity, so that the HER performance is improved, and excellent catalytic hydrogen evolution performance is shown. And 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 field of hydrogen evolution, but also provides a new idea for synthesis of preparing a 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, and 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. The electrocatalysis and the photoelectrocatalysis are one of the important sources of hydrogen, and the high-performance electrocatalysis is the core of water electrolysis and photoelectrocatalysis. At present, the water electrolysis catalyst widely applied mainly adopts noble metal Pt and alloy thereof as HER catalyst, but the high cost and resource scarcity of Pt-based HER catalyst seriously restrict the wide application of the Pt-based HER catalyst as HER catalyst. The search for inexpensive, highly active, acid stable hydrogen evolution catalysts has been a current focus of research.
The two-dimensional transition metal sulfide has the formula MX2M is a transition metal element (e.g., molybdenum, tungsten, niobium, rhenium, titanium), and X is a chalcogen element (e.g., sulfur, selenium, tellurium). The strong spin-orbit coupling effect and the structural diversity of the material endow the material with a plurality of novel physical properties, such as WTE in a few layers of 1Td phase2The quantum spin Hall effect is observed, and MoS of 2H phase is arranged in a minority layer2And NbSe2In the above, an ixin superconductivity was observed. These findings make MX2 material a hotspot for current condensed state physics and material science research. Also, generally, a single layer of transition metal sulfide exhibits an X-M-X sandwich structure. The van der waals forces between layers are weak, whereas there are strong covalent bonds in the plane. Bulk transition metal sulfides can be exfoliated into single or multi-layered nanosheets like graphene. The band gap of many two-dimensional transition metal sulfides is in the range of 1-2 eV, and increases with the decrease in the number of layers. Some two-dimensional transition metal sulfides, such as chalcogenides of molybdenum and tungsten, have an indirect bandgap when the material is a multilayer structure and a direct bandgap when the material is exfoliated into a single layer. The single-layer two-dimensional transition metal sulfide has a direct band gap energy band structure, so that the light emission efficiency can be improved, and the opportunity is brought to the preparation of a high-performance photoelectric device.
More notably, a transition metal disulfide, such as MoS2、WS2、MoSe2And WSe2The use of Hydrogen Evolution Reactions (HER) has been catalyzed by many scientists. The transition metal disulfide compound has unique catalytic action and high earth content, and the method becomes a simple and low-cost method for producing hydrogenFormula (II) is shown. Although WS2Is a stable high activity catalyst for HER, but further improvements are needed, especially for WS prepared by traditional methods2The catalytic performance is not ideal, and many researchers build special structures and compound with other materials to improve the catalytic performance. However, the traditional methods for preparing the composite catalyst mainly comprise methods and processes such as a step-by-step solvothermal method, a CVD method, a high-temperature calcination method and the like, and are high in cost, complex and tedious.
Therefore, how to find a simple compounding mode and find a more suitable tungsten disulfide composite catalyst can change WS by using a simple method2The catalytic activity of the compound is suitable for industrial popularization and application, and becomes one of the problems to be solved urgently by a plurality of front-line researchers and scientific research type enterprises.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a tungsten disulfide/molybdenum disulfide/graphene composite material, a preparation method and an application thereof, and in particular, a tungsten disulfide/molybdenum disulfide/graphene composite material having a layered structure. The tungsten disulfide composite material provided by the invention has a specific layered structure, greatly improves the capacity of tungsten disulfide catalytic activity, thereby improving HER performance, and has the advantages of simple preparation method, mild conditions, easy operation and low cost, and can better promote the commercial application of a 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, the flaky molybdenum disulfide and the graphene sheet to form a layered structure.
Preferably, the flaky molybdenum disulfide and the flaky tungsten disulfide are compounded on the graphene sheet layer;
the flaky molybdenum disulfide comprises a molybdenum disulfide micro-nano sheet;
the flaky tungsten disulfide comprises a tungsten disulfide micro-nano sheet;
the graphene sheet comprises a graphene micro-nano sheet;
the mass ratio of the graphene sheet to the sheet-shaped 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;
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 sheet-shaped 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 composite includes a laminate.
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 flaky layer;
the composite material has a wrinkled micro-topography;
the folds comprise mountain folds and/or wave folds;
gaps are reserved 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 sheet;
dispersing and mixing expanded graphite, a second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a graphene micro-nano sheet;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A;
2) re-dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, the sulfur source, the third surfactant and water obtained in the previous step to obtain a mixed solution B;
3) and after mixing the mixed solution B and the mixed solution A obtained in the step again, adjusting 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, respectively;
the mass ratio of the molybdenum disulfide powder to water is (0.5-3): 100, respectively;
the second surfactant comprises one or more of ethylenediamine, octadecyl trimethyl ammonium chloride, polyetherimide, hexadecyl dimethyl allyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl hydroxyethyl ammonium chloride and dodecyl trimethyl ammonium chloride;
the mass ratio of the expanded graphite to the second surfactant is (1-5): 100, respectively;
the mass ratio of the expanded graphite to water is (0.5-3): 100, respectively;
the dispersing and dispersing mixing mode comprises ultrasonic stirring and dispersing;
the centrifugation process specifically comprises the following steps: firstly centrifuging at low speed to obtain supernatant, and then centrifuging at high speed to obtain subnatant;
the centrifugation step further comprises a drying step.
Preferably, the ultrasonic frequency of the ultrasonic stirring dispersion is 20-40 KHz;
the rotating speed of the ultrasonic stirring dispersion 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 h;
the grinding time is 30-60 min;
the rotation speed of the grinding is 1000-1500 rpm;
the fineness of the graphene micro-nano sheet and the fineness of the molybdenum disulfide micro-nano sheet are 10-30 mu m;
the molar ratio of the tungsten hexachloride to the ammonium tungstate is (0.2-1): 1;
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 moles of the tungsten hexachloride and the ammonium tungstate to the sulfur source is 1: (2.5-3);
the sulfur source comprises 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 sheet to the third surfactant is (1-10): 100, respectively;
the mode of re-dispersion is ultrasonic dispersion;
the re-dispersing time is 10-30 min;
the mode of mixing again is slow addition;
the pH value is 5-7;
the reaction temperature 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 or the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by the preparation method in any 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; and compounding the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheet to form a layered structure. Compared with the prior art, the invention aims at the existing WS2Need to be further improved, and WS prepared by the conventional method2The catalytic performance is not ideal, and the catalytic performance is improved by constructing a special structure and compounding with other materials. And the problems of complex and fussy method and process and high cost exist.
The tungsten disulfide composite material provided by the invention is a tungsten disulfide/molybdenum disulfide/graphene layered composite material which can provide more active sites and higher active surface area and greatly improve the capacity of tungsten disulfide catalytic activity by virtue of electrostatic adsorption, thereby improving HER performance, showing excellent catalytic hydrogen evolution performance, and effectively solving the defect that a single transition metal tungsten disulfide has catalytic activity only at the boundary and has no catalytic activity on the surface.
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 conditions, easiness in operation and low cost, and can better promote the commercial application of the tungsten disulfide composite catalyst. The invention not only provides an excellent catalyst for the field of hydrogen evolution, but also solves the problem that the traditional hydrogen evolution catalyst is mainly noble metal such as Pt and the like, has high cost and hinders large-scale application and commercial development, and provides a new idea for synthesis of preparing the composite two-dimensional catalyst.
Experimental results show that the tungsten disulfide/molybdenum disulfide/graphene composite catalyst prepared by the invention has a smaller Tafel slope (104mV/dec) and shows excellent hydrogen evolution catalytic performance.
Drawings
Fig. 1 is a simplified flow chart of a specific preparation process of a tungsten disulfide/molybdenum disulfide/graphene composite material according to an embodiment of the present invention;
fig. 2 is a TEM transmission electron micrograph 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 the tungsten disulfide micro-nano sheet prepared in example 3 of the present invention;
figure 5 is a polarization plot of a catalyst made from a tungsten disulfide composite made according to example 1 of the present invention and a catalyst made from tungsten disulfide made according to example 3;
figure 6 is a tafel plot of a catalyst made from a tungsten disulfide composite made according to example 1 of the present invention and a catalyst made from tungsten disulfide made according to example 3;
figure 7 is a graph of the electrochemical impedance of a catalyst made from the tungsten disulfide composite produced in example 1 of the present invention and a catalyst made from the tungsten disulfide produced in example 3.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially 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 their purity, and the present invention preferably employs analytical grade 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, the flaky molybdenum disulfide and the graphene sheet to form a layered structure.
The specific structural relationship of the composite is not particularly limited in principle, and a person skilled in the art can select and adjust the specific structural relationship according to the actual application condition, the product requirement and the quality requirement, so that more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and further the HER performance is improved, and the flaky molybdenum disulfide and the flaky tungsten disulfide are preferably compounded on the graphene sheet layer; more specifically, the flaky molybdenum disulfide and the flaky tungsten disulfide are preferably compounded on the graphene sheet layer and/or the flaky molybdenum disulfide and the flaky tungsten disulfide are compounded on the graphene sheet layer in a laminated manner, more preferably, the flaky molybdenum disulfide and the flaky tungsten disulfide are compounded on the graphene sheet layer in a laminated manner, and more specifically, the flaky molybdenum disulfide is preferably compounded between the flaky tungsten disulfide and the graphene sheet layer.
According to the invention, different surfactants are used for modifying molybdenum disulfide and graphene, so that the surfaces of molybdenum disulfide sheets and graphene sheets are respectively provided with negative charges and positive charges, when the modified molybdenum disulfide sheets and graphene sheets are mixed, molybdenum disulfide is loaded on the graphene sheets, and after a tungsten source is added, tungsten positive ions are loaded on the other side of molybdenum disulfide through the action of charges (since the positive charges on the surface of graphene are repelled with the tungsten positive ions, most of the tungsten positive ions are not loaded on the surface of the graphene sheets), and tungsten disulfide nanosheets are formed through hydrothermal reaction, so that the tungsten disulfide/molybdenum disulfide/graphene composite material is obtained.
The invention has no particular limitation on the specific mode of compounding in principle, and a person skilled in the art can select and adjust the specific mode according to the actual application condition, the product requirement and the quality requirement.
The invention has no particular limitation on the specific type of the composite in principle, and a person skilled in the art can select and adjust the composite according to the actual application situation, the product requirement and the quality requirement.
The specific parameters of the flaky molybdenum disulfide are not particularly limited in principle, and a person skilled in the art can select and adjust the flaky molybdenum disulfide according to the actual application condition, the product requirement and the quality requirement. The flake diameter of the flake molybdenum disulfide is preferably 5-10 μm, more preferably 6-9 μm, and more preferably 7-8 μm. The thickness of the flaky molybdenum disulfide is preferably 5-12 nm, more preferably 6-11 nm, more preferably 7-10 nm, and more preferably 8-9 nm.
The specific parameters of the flaky tungsten disulfide are not particularly limited in principle, and a person skilled in the art can select and adjust the flaky tungsten disulfide according to the actual application condition, the product requirement and the quality requirement. The flake diameter of the flake tungsten disulfide is preferably 2-7 μm, more preferably 3-6 μm, and preferably 4-5 μm. The thickness of the flaky tungsten disulfide is preferably 1-12 nm, more preferably 3-10 nm, and even more preferably 5-8 nm.
The specific parameters of the graphene sheet are not particularly limited in principle, and a person skilled in the art can select and adjust the specific parameters according to the actual application condition, the product requirements and the quality requirements. The sheet diameter of the graphene sheet is preferably 5-15 μm, more preferably 7-13 μm, and most preferably 9-11 μm. The thickness of the graphene sheet is preferably 1-10 nm, more preferably 3-8 nm, and more preferably 5-6 nm.
The proportion of the graphene sheets in the composite material is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and further the HER performance is improved, 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 proportion of the flaky molybdenum disulfide in the composite material is not particularly limited in principle, and a person skilled in the art can select and adjust the flaky molybdenum disulfide according to the actual application condition, the product requirement and the quality requirement, so that more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and the HER performance is further improved, 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 the actual application situation, the product requirements and the quality requirements. Gaps are preferably arranged among the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheets.
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 sheet;
dispersing and mixing expanded graphite, a second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a graphene micro-nano sheet;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A;
2) re-dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, the sulfur source, the third surfactant and water obtained in the previous step to obtain a mixed solution B;
3) and after mixing the mixed solution B and the mixed solution A obtained in the step again, adjusting 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 solution, and then centrifuging and grinding to obtain a molybdenum disulfide micro-nano sheet;
dispersing and mixing expanded graphite, a second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a graphene micro-nano sheet;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A.
The kind of the first surfactant is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application situation, product requirements and quality requirements, and the present invention provides more active sites and higher active surface area to better ensure the specific structure and morphology of the composite material, thereby improving HER performance, and the first surfactant preferably includes one or more of sodium dodecyl benzene sulfonate, N-lauroyl sarcosine sodium, sodium dodecyl sulfate, sodium fatty alcohol ether sulfate and alcohol acyl phosphate, and more preferably includes sodium dodecyl benzene sulfonate, N-lauroyl sarcosine sodium, 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 actual application conditions, product requirements and quality requirements, more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and further the HER performance is improved, and 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 (2-4): 100, more preferably (2.5 to 3.5): 100.
the proportion of the water is not particularly limited in principle, and a person skilled in the art can select and adjust the proportion according to the actual application situation, the product requirement and the quality requirement, so that the specific structure and morphology of the composite material are better ensured, more active sites and higher active surface area are provided, the HER performance is further improved, and the preferred mass ratio of the molybdenum disulfide powder to the water is (0.5-3): 100, more preferably (1-2.5): 100, more preferably (1.5-2): 100.
the kind of the second surfactant is not particularly limited in principle, and can be selected and adjusted by the skilled in the art according to the actual application situation, the product requirements and the 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, and further improving HER performance, the second surfactant comprises one or more of ethylenediamine, octadecyltrimethylammonium chloride, polyetherimide, hexadecyldimethylallylammonium chloride, tetradecyldimethylbenzylammonium chloride, dodecyldimethylhydroxyethylammonium chloride and dodecyltrimethylammonium chloride, and more preferably ethylenediamine, octadecyltrimethylammonium chloride, polyetherimide, hexadecyldimethylallylammonium chloride, tetradecyldimethylbenzylammonium chloride, dodecyldimethylhydroxyethylammonium chloride or dodecyltrimethylammonium chloride.
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 actual application conditions, product requirements and quality requirements, more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and further the HER performance is improved, 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 (2-4): 100, more preferably (2.5 to 3.5): 100.
the proportion of the water is not particularly limited in principle, and a person skilled in the art can select and adjust the proportion according to the actual application situation, the product requirement and the quality requirement, 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 the HER performance, and the preferred mass ratio of the expanded graphite to the water is (0.5-3): 100, more preferably (1-2.5): 100, more preferably (1.5-2): 100.
the invention has no particular limitation on the dispersing and dispersing mixing mode in principle, and a person skilled in the art can select and adjust the dispersing and dispersing mixing mode according to the actual application situation, the product requirement and the quality requirement. The mode of dispersive mixing according to the invention preferably comprises ultrasonic agitation and dispersion.
The specific parameters of the ultrasonic stirring dispersion are not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application condition, the product requirement and the quality requirement, the specific structure and morphology of the composite material are better ensured, more active sites and higher active surface area are provided, and the HER performance is further improved, and the ultrasonic frequency of the ultrasonic stirring dispersion is preferably 20-40 KHz, more preferably 22-38 KHz, more preferably 25-35 KHz, and more preferably 28-32 KHz. The rotation speed of the ultrasonic stirring dispersion is preferably 300-500 rpm, more preferably 330-480 rpm, more preferably 350-450 rpm, and more preferably 380-430 rpm. The ultrasonic stirring and dispersing time is preferably 120-360 min, more preferably 150-330 min, more preferably 180-300 min, and more preferably 210-270 min.
The invention has no special limitation on the specific process and parameters of the centrifugation in principle, and a person skilled in the art can select and adjust the specific process and parameters according to the actual application condition, the product requirement and the quality requirement, 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 the HER performance, and the centrifugation process specifically comprises the following steps: the supernatant is obtained by low-speed centrifugation, and the supernatant is obtained by high-speed centrifugation. Wherein the rotation speed of the low-speed centrifugation is preferably 500-1000 rpm, more preferably 600-900 rpm, and more preferably 700-800 rpm. The time of the low-speed centrifugation is preferably 3-5 min, more preferably 3.3-4.7 min, more preferably 3.6-4.4 min, and more preferably 3.9-4.1 min. The rotating speed of the high-speed centrifugation is preferably 3000-5000 rpm, more preferably 3300-4700 rpm, more preferably 3600-4400 rpm, and more preferably 3900-4100 rpm. The high-speed centrifugation time is preferably 5-10 min, more preferably 6-9 min, and more preferably 7-8 min.
The invention 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. Specifically, the drying temperature is preferably 40-80 ℃, more preferably 45-75 ℃, more preferably 50-70 ℃, and more preferably 55-65 ℃. The drying time is preferably 6-24 hours, more preferably 9-21 hours, and more preferably 12-18 hours.
The specific process and parameters of the grinding are not particularly limited in principle, and a person skilled in the art can select and adjust the grinding time according to the actual application condition, the product requirement and the quality requirement, so that more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and the HER performance is improved, and the grinding time is preferably 30-60 min, more preferably 35-55 min, and more preferably 40-50 min. The rotation speed of the grinding is preferably 1000-1500 rpm, more preferably 1100-1400 rpm, and more preferably 1200-1300 rpm.
The fineness of the ground graphene micro-nano sheet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, more active parts and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and further the HER performance is improved, and the fineness of the graphene micro-nano sheet is preferably 10-30 μm, more preferably 12-28 μm, more preferably 15-25 μm, and more preferably 17-22 μm.
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 actual application conditions, product requirements and quality requirements.
The molar ratio of the tungsten hexachloride to the ammonium tungstate is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and quality requirements, the specific structure and morphology of the composite material are better guaranteed, more active sites and higher active surface area are provided, and the HER performance is further improved, 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.
according to the invention, the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, the sulfur source, the third surfactant and water obtained in the above steps are dispersed again to obtain a mixed solution B.
The invention is not particularly limited in the kind of the sulfur source in principle, and the skilled person can select and adjust the sulfur source 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.
The addition amount of the sulfur source is not particularly limited in principle, and a person skilled in the art can select and adjust the sulfur source according to the actual application situation, the product requirements and the 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, the HER performance is further improved, and the molar ratio of the total molar number of the tungsten hexachloride and the ammonium tungstate to the molar number of the sulfur source is preferably 1: (2.5-3), more preferably 1: (2.6-2.9), more preferably 1: (2.7-9).
The ratio 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 by a person skilled in the art according to actual application conditions, product requirements and quality requirements, more active parts and higher active surface area are provided for better ensuring the specific structure and morphology of a composite material, and further the HER performance is improved, the mass ratio of the molybdenum disulfide micro-nano sheet to the graphene micro-nano sheet is preferably 10 (0.5-2), and more preferably 10: (0.8 to 1.7), more preferably 10: (0.8 to 1.7).
The kind of the third surfactant is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the practical application, product requirements and quality requirements, and the present invention provides more active sites and higher active surface area to better ensure the specific structure and morphology of the composite material, thereby improving HER performance, and the third surfactant preferably includes one or more of cetyltrimethylammonium bromide, octadecene, polyvinylpyrrolidone and F127, more preferably cetyltrimethylammonium bromide, octadecene, polyvinylpyrrolidone or F127.
In the invention, the mass ratio of the molybdenum disulfide micro-nano sheet to the third surfactant is not particularly limited in principle, and a person skilled in the art can select and adjust the mass ratio according to the actual application condition, the product requirement and the quality requirement, so that more active parts and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and further the HER performance is improved, and the mass ratio of the molybdenum disulfide micro-nano sheet to the third surfactant is preferably (1-10): 100, more preferably (3-8): 100, more preferably (5-6): 100.
the redispersion process and parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the redispersion process and parameters according to actual application conditions, product requirements and quality requirements, the redispersion method preferably adopts ultrasonic dispersion to better ensure the specific structure and morphology of the composite material, provides more active sites and higher active surface area, and further improves HER performance, and more specifically, 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, after the mixed solution B and the mixed solution A obtained in the step are mixed again, the pH value is adjusted, and after reaction, the tungsten disulfide/molybdenum disulfide/graphene composite material is obtained.
The pH value is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application situation, the product requirements and the quality requirements, more active sites and higher active surface area are provided for better ensuring the specific structure and morphology of the composite material, and the HER performance is further improved, wherein the pH value is preferably 5-7, more preferably 5.3-6.7, more preferably 5.6-6.4, and more preferably 5.9-6.1.
The reaction parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the reaction parameters according to actual application conditions, product requirements and quality requirements, so that the specific structure and morphology of the composite material are better guaranteed, more active sites and higher active surface area are provided, the HER performance is further improved, and the reaction temperature is preferably 160-240 ℃, more preferably 170-230 ℃, more preferably 180-220 ℃, and more preferably 190-210 ℃. More specifically, the reaction time is preferably 12-24 hours, more preferably 14-22 hours, and more preferably 16-20 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 liquid; then centrifuging at a low speed, taking the upper layer liquid, centrifuging at a high speed, taking the lower layer, and finally drying in vacuum, drying and grinding 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 centrifuging at a low speed, taking supernatant, centrifuging at a high speed, taking a lower layer, and finally drying in vacuum, drying and grinding to form the graphene micro-nano sheet;
adding tungsten hexachloride and ammonium tungstate with certain mass into deionized water, and magnetically stirring to form a mixed solution A;
adding molybdenum disulfide micro-nano sheets, graphene micro-nano sheets, a sulfur source and a third surfactant with certain mass into water, and performing ultrasonic dispersion to form a mixed solution B;
and slowly adding the mixed solution B into the solution A, adjusting the pH value, transferring the mixed solution B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating and 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 simplified flow chart of a specific preparation process of a tungsten disulfide/molybdenum disulfide/graphene composite material according to an embodiment of the present invention.
The invention also provides the application of the tungsten disulfide/molybdenum disulfide/graphene composite material or the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by the preparation method in any 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, the tungsten disulfide composite material has a specific layered structure, particularly, the tungsten disulfide/molybdenum disulfide/graphene orderly-laminated composite material can be formed, more active sites and higher active surface area can be provided, the capacity of tungsten disulfide catalytic activity is greatly improved, the HER performance is improved, excellent catalytic hydrogen evolution performance is shown, and the defect that a single transition metal tungsten disulfide has catalytic activity only at the boundary and has no catalytic activity on the surface is effectively overcome.
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 conditions, easiness in operation and low cost, and can better promote the commercial application of the tungsten disulfide composite catalyst. The invention not only provides an excellent catalyst for the field of hydrogen evolution, but also solves the problem that the traditional hydrogen evolution catalyst is mainly noble metal such as Pt and the like, has high cost and hinders large-scale application and commercial development, and provides a new idea for synthesis of preparing the composite two-dimensional catalyst.
Experimental results show that the tungsten disulfide/molybdenum disulfide/graphene composite catalyst prepared by the invention has a smaller Tafel slope (104mV/dec) and shows excellent hydrogen evolution catalytic performance.
For further illustration of the present invention, the tungsten disulfide/molybdenum disulfide/graphene composite material and the preparation method and application thereof are described in detail below with reference to the following examples, but it should be understood that the examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, but 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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then putting the molybdenum disulfide micro-nano sheet in vacuum drying at 60 ℃ overnight for drying and grinding to form the molybdenum disulfide micro-nano sheet.
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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then, drying and grinding the graphene micro-nano sheet in vacuum drying at 60 ℃ overnight to form the graphene micro-nano sheet.
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 solution A;
adding 0.7439g of molybdenum disulfide micro-nano sheet, 0.0744g of graphene micro-nano sheet, 2.2836g of thiourea and a certain mass of polyvinylpyrrolidone into 36ml of deionized water, and performing ultrasonic dispersion for 30min to form a mixed solution B;
and slowly adding the mixed solution B into the solution A, adjusting the pH value to 5-7, transferring the mixed solution B 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 embodiment 1 of the present 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 and subsequent fig. 4, the tungsten disulfide/molybdenum disulfide/graphene composite material prepared by the present invention has an obvious laminated structure, the layered tungsten disulfide micro-nano sheet, the layered molybdenum disulfide micro-nano sheet, and the graphene sheet are laminated in an ordered manner, the three layered materials have a micron-sized sheet diameter and a nano-sized thickness, and the composite material has a mountain-vein-like or wave-like folded microstructure as a whole. Further based on common sense judgment, the sheet-shaped tungsten disulfide, the sheet-shaped molybdenum disulfide and the graphene sheet have gaps, and more gaps are irregularly shaped.
The performance of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in embodiment 1 of the invention is detected. For specific detection results, see comparative detection results in subsequent example 3.
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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then putting the molybdenum disulfide micro-nano sheet in vacuum drying at 60 ℃ overnight for drying and grinding to form the molybdenum disulfide micro-nano sheet.
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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then, drying and grinding the graphene micro-nano sheet in vacuum drying at 60 ℃ overnight to form the graphene micro-nano sheet.
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 solution A;
adding 0.7439g of molybdenum disulfide micro-nano sheet, 0.0744g of graphene micro-nano sheet, 2.2836g of thiourea and a certain mass of polyvinylpyrrolidone into 36ml of deionized water, and performing ultrasonic dispersion for 30min to form a mixed solution B;
and slowly adding the mixed solution B into the solution A, adjusting the pH value to 5-7, transferring the mixed solution B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 160 ℃, 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 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 invention has an obvious laminated structure, the layered tungsten disulfide micro-nano sheet, the layered molybdenum disulfide micro-nano sheet and the graphene sheet are laminated together in an ordered manner, the three layered materials have micron-scale sheet diameters and nanometer-scale thicknesses, and the composite material has a mountain-wave or wave-like folded micro-morphology as a whole. Further based on common sense judgment, the sheet-shaped tungsten disulfide, the sheet-shaped molybdenum disulfide and the graphene sheet have gaps, and more gaps are irregularly shaped.
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 solution A;
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;
and slowly adding the mixed solution B into the solution A, then transferring the mixed solution B 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 image of the tungsten disulfide micro-nano sheet prepared in example 3 of the present invention.
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 were subjected to comparative performance detection.
Preparation of the electrodes
The prepared composite material catalyst is coated on a glassy carbon electrode to be used as an electrocatalytic hydrogen production electrode for electrocatalytic hydrogen evolution.
And taking the rotary disc glassy carbon electrode as a working electrode, polishing and pre-cleaning the surface of the rotary disc glassy carbon electrode by using an alumina solution, and naturally drying the rotary disc glassy carbon electrode in the sun. Mixing the composite catalyst with an alcohol aqueous solution (V/V is 7:3), ultrasonically dispersing uniformly (ultrasonic uniformity is required for each use), measuring 14.5 mu L of mixed solution by using a digital electric pipettor, coating the mixed solution on a rotating disc glassy carbon electrode, naturally airing in a clean environment, and carrying out electrochemical test.
Electrochemical test method
The electrochemical performance of the catalyst was measured by an electrochemical workstation. The electrochemical workstation is connected with the H-shaped electrolytic cell through a three-electrode system, the electrolyte is 1M KOH aqueous solution, meanwhile, external computer equipment transmits electric signals to a computer in time, and the performance index of the material is obtained by analyzing specific data.
Referring to fig. 5, fig. 5 is a polarization plot of a catalyst made from the tungsten disulfide composite produced in example 1 and a catalyst made from the tungsten disulfide produced in example 3 in accordance with 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 made from the tungsten disulfide composite prepared in example 1 and the catalyst made from the tungsten disulfide prepared in example 3 of the present invention.
As can be seen in FIG. 6, the Tafel slope is used as a benchmark for evaluating the intrinsic properties of the electrocatalyst for its superiority and inferiority, the Tafel slopes (104 and 207mV/dec) for the catalyst prepared in example 1 and the pure tungsten disulfide catalyst samples. The faster the current density of the catalyst prepared in example 1 increased with increasing overpotential, the faster the hydrogen evolution reaction rate could be easily achieved, the smaller the tafel slope, indicating that the catalyst prepared in example 1 has superior catalytic performance.
And comparing the electrochemical performance of the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in the embodiment 1 of the invention with that of the tungsten disulfide material prepared in the embodiment 3.
Referring to fig. 7, fig. 7 is a graph of the electrochemical impedance of a catalyst made from the tungsten disulfide composite produced in example 1 and a catalyst made from the tungsten disulfide produced in example 3 in accordance with the present invention.
As can be seen from fig. 7, the radius of the semi-circle 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 a 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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then putting the molybdenum disulfide micro-nano sheet in vacuum drying at 60 ℃ overnight for drying and grinding to form the molybdenum disulfide micro-nano sheet.
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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then, drying and grinding the graphene micro-nano sheet in vacuum drying at 60 ℃ overnight to form the graphene micro-nano sheet.
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 solution A;
0.7439g of molybdenum disulfide micro-nano sheet, 0.0372g of graphene micro-nano sheet, 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;
and slowly adding the mixed solution B into the solution A, adjusting the pH value to 5-7, transferring the mixed solution B 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 embodiment 4 of the invention is characterized.
The result shows that the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 4 has a similar layered morphology of ordered 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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then putting the molybdenum disulfide micro-nano sheet in vacuum drying at 60 ℃ overnight for drying and grinding to form the molybdenum disulfide micro-nano sheet.
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 the upper layer solution, centrifuging at high speed of 5000r/min for 10min, collecting the lower layer solution, and washing; and then, drying and grinding the graphene micro-nano sheet in vacuum drying at 60 ℃ overnight to form the graphene micro-nano sheet.
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 solution A;
0.7439g of molybdenum disulfide micro-nano sheet, 0.1498g of graphene micro-nano sheet, 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, adjusting the pH value to 5-7, transferring the mixed solution B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 160 ℃, 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 embodiment 5 of the present invention is characterized.
The result shows that the tungsten disulfide/molybdenum disulfide/graphene composite material prepared in example 5 has a similar layered morphology of ordered laminated composite.
The above detailed description of the tungsten disulfide/molybdenum disulfide/graphene composite material with a layered structure, the preparation method and the application thereof, and the specific examples applied herein illustrate the principles and embodiments of the present invention, and the above description of the examples is only provided to help understand the method and the core idea of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any method in combination. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention 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 languages of the claims.
Claims (10)
1. A tungsten disulfide/molybdenum disulfide/graphene composite material, characterized in that the composite material has a layered structure;
and compounding the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheet to form a layered structure.
2. The composite material of claim 1, wherein the sheet-like molybdenum disulfide and tungsten disulfide are composited on the graphene sheet layer;
the flaky molybdenum disulfide comprises a molybdenum disulfide micro-nano sheet;
the flaky tungsten disulfide comprises a tungsten disulfide micro-nano sheet;
the graphene sheet comprises a graphene micro-nano sheet;
the mass ratio of the graphene sheet to the sheet-shaped 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;
the sheet diameter of the graphene sheet is 5-15 mu m.
3. The composite material of claim 1, wherein the graphene sheets have a thickness of 1 to 10 nm;
the sheet diameter of the sheet-shaped 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 composite includes a laminate.
4. The composite material of claim 1, wherein the compositing is 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 flaky layer;
the composite material has a wrinkled micro-topography;
the folds comprise mountain folds and/or wave folds;
gaps are reserved among the flaky tungsten disulfide, the flaky molybdenum disulfide and the graphene sheets.
5. A preparation method of a tungsten disulfide/molybdenum disulfide/graphene composite material is characterized by 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 sheet;
dispersing and mixing expanded graphite, a second surfactant and water to obtain a dispersion liquid, and centrifuging and grinding to obtain a graphene micro-nano sheet;
mixing tungsten hexachloride, ammonium tungstate and water to obtain a mixed solution A;
2) re-dispersing the molybdenum disulfide micro-nano sheet, the graphene micro-nano sheet, the sulfur source, the third surfactant and water obtained in the previous step to obtain a mixed solution B;
3) and after mixing the mixed solution B and the mixed solution A obtained in the step again, adjusting the pH value, and reacting to obtain the tungsten disulfide/molybdenum disulfide/graphene composite material.
6. The method of claim 5, wherein the first surfactant comprises one or more of sodium dodecylbenzenesulfonate, sodium N-lauroyl sarcosinate, sodium lauryl 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, respectively;
the mass ratio of the molybdenum disulfide powder to water is (0.5-3): 100, respectively;
the second surfactant comprises one or more of ethylenediamine, octadecyl trimethyl ammonium chloride, polyetherimide, hexadecyl dimethyl allyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl hydroxyethyl ammonium chloride and dodecyl trimethyl ammonium chloride;
the mass ratio of the expanded graphite to the second surfactant is (1-5): 100, respectively;
the mass ratio of the expanded graphite to water is (0.5-3): 100, respectively;
the dispersing and dispersing mixing mode comprises ultrasonic stirring and dispersing;
the centrifugation process specifically comprises the following steps: firstly centrifuging at low speed to obtain supernatant, and then centrifuging at high speed to obtain subnatant;
the centrifugation step further comprises a drying step.
7. The preparation method according to claim 6, wherein the ultrasonic frequency of the ultrasonic stirring dispersion is 20-40 KHz;
the rotating speed of the ultrasonic stirring dispersion 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 preparation method according to claim 6, wherein the drying temperature is 40-80 ℃;
the drying time is 6-24 h;
the grinding time is 30-60 min;
the rotation speed of the grinding is 1000-1500 rpm;
the fineness of the graphene micro-nano sheet and the fineness of the molybdenum disulfide micro-nano sheet are 10-30 mu m;
the molar ratio of the tungsten hexachloride to the ammonium tungstate is (0.2-1): 1;
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 moles of the tungsten hexachloride and the ammonium tungstate to the sulfur source is 1: (2.5-3);
the sulfur source comprises one or more of sulfur, thiourea, thiol, ammonium trisulfide, thioacetamide and L-cysteine.
9. The method of 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 sheet to the third surfactant is (1-10): 100, respectively;
the mode of re-dispersion is ultrasonic dispersion;
the re-dispersing time is 10-30 min;
the mode of mixing again is slow addition;
the pH value is 5-7;
the reaction temperature is 160-240 ℃;
the reaction time is 12-24 h.
10. The application 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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