CN108607582A - Molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, preparation method and application - Google Patents
Molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, preparation method and application Download PDFInfo
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- CN108607582A CN108607582A CN201810529922.XA CN201810529922A CN108607582A CN 108607582 A CN108607582 A CN 108607582A CN 201810529922 A CN201810529922 A CN 201810529922A CN 108607582 A CN108607582 A CN 108607582A
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- graphene oxide
- molybdenum disulfide
- reproducibility
- composite material
- nickel
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 141
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 103
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 100
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 20
- 239000005864 Sulphur Substances 0.000 claims description 20
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 239000004575 stone Substances 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
- 238000005406 washing Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 231100001231 less toxic Toxicity 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 oxygen Graphite alkene Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical group [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
An embodiment of the present invention provides molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, preparation method and applications, wherein molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, using reproducibility graphene oxide as substrate, molybdenum disulfide nano sheet is scattered in reproducibility graphene oxide substrate, and nickel nano particle is dispersed on reproducibility graphene oxide substrate and molybdenum disulfide nano sheet.Molybdenum disulfide provided by the invention/reproducibility graphene oxide/nickel nano particle composite material has evolving hydrogen reaction catalytic activity simultaneously in acidic electrolysis bath and alkaline electrolyte, and the evolving hydrogen reaction catalytic activity especially in alkaline electrolyte is more preferable.Meanwhile preparation method provided by the invention, simple and practicable, raw material is cheap and easy to get, has good economic prospect.
Description
Technical field
The present invention relates to evolving hydrogen reaction catalyst preparation technical fields, and stone is aoxidized more particularly to molybdenum disulfide/reproducibility
Black alkene/nickel nano particle composite material, preparation method and application.
Background technology
Hydrogen Energy is cleaned, efficiently with it, becomes most promising regenerative resource.Water electrolysis is the weight for obtaining Hydrogen Energy
One of means are wanted, wherein evolving hydrogen reaction occurs in cathode.The overpotential of evolving hydrogen reaction is higher, and platinum class noble metal is generally needed to be catalyzed
Agent.However, noble metal is of high cost, resource is limited, its application in evolving hydrogen reaction is limited.Therefore, prepare it is efficient, low at
Originally, the high evolving hydrogen reaction catalyst of reserves is very necessary.
The nano-particle of transition metal elemental nickel has certain evolving hydrogen reaction catalytic activity in alkaline medium, but in acidity
Catalytic performance in electrolyte is poor.In addition, nickel nano particle is easily agglomerated into bulky grain in synthesis, make number of active sites
It reduces, catalytic performance reduces.
Invention content
The embodiment of the present invention is designed to provide one kind in acidic electrolysis bath and alkaline electrolyte while having liberation of hydrogen
The active molybdenum disulfide of catalytic reaction/reproducibility graphene oxide/nickel nano particle composite material.While the present invention also provides
The preparation method of molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material and its application.Specific technical solution
It is as follows：
Present invention firstly provides a kind of molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite materials, with also
Originality graphene oxide is substrate, and molybdenum disulfide nano sheet is scattered in reproducibility graphene oxide substrate, nickel nano particle point
It is dispersed on reproducibility graphene oxide substrate and molybdenum disulfide nano sheet.
The present invention also provides the systems of molybdenum disulfide above-mentioned/reproducibility graphene oxide/nickel nano particle composite material
Preparation Method, including：
(1), graphene oxide is dispersed in water, obtains graphene oxide dispersion；
(2), molybdenum source, sulphur source are mixed with graphene oxide dispersion, obtains the first reaction mixture；
(3), first reaction mixture is divided after reaction hydro-thermal reaction 18-30 hours at 180 DEG C -220 DEG C
From, washing, obtain molybdenum disulfide/reproducibility graphene oxide composite material；
(4), the molybdenum disulfide/reproducibility graphene oxide composite material is scattered in organic solvent, obtains two sulphur
Change molybdenum/reproducibility graphene oxide composite material dispersion liquid；
(5), nickel source and hydrazine hydrate are added into the molybdenum disulfide/reproducibility graphene oxide composite material dispersion liquid
Afterwards, it is 8-10 to adjust pH value, obtains the second reaction mixture；
(6), second reaction mixture is reacted 0.5-3 hours at 50-70 DEG C, detaches, washs after reaction,
Obtain molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material.
In some embodiments of preparation method provided by the invention, the molar ratio of sulphur source and molybdenum source is (2.5-10)：
1；The molal quantity of molybdenum source and the ratio of graphite oxide quality are (0.033-0.1):1mol/g.
In some embodiments of preparation method provided by the invention, the molybdenum source is in sodium molybdate, ammonium molybdate
One kind or combinations thereof；The one kind or combinations thereof of the sulphur source in thiocarbamide, thioacetamide.
In some embodiments of preparation method provided by the invention, the nickel source is selected from nickel sulfate, nickel nitrate, chlorination
One kind in nickel or combinations thereof.
In some embodiments of preparation method provided by the invention, molal quantity and the molybdenum disulfide/reproducibility of nickel source
The ratio of the quality of graphene oxide composite material is (0.0018-0.007)：1mol/g.
In some embodiments of preparation method provided by the invention, volume and the molybdenum disulfide/reproducibility of hydrazine hydrate
The ratio of the quality of graphene oxide composite material is (0.02-0.03)：1mL/mg.
In some embodiments of preparation method provided by the invention, the organic solvent is in ethylene glycol, ethyl alcohol
One kind or combinations thereof.
The present invention also provides molybdenum disulfide above-mentioned/reproducibility graphene oxide/nickel nano particle composite material conducts
The purposes of evolving hydrogen reaction catalyst.
In certain specific embodiments of the invention, wherein the molybdenum disulfide/reproducibility graphene oxide/nickel nanometer
Particle composite material is used as evolving hydrogen reaction catalyst in alkaline electrolyte.
Molybdenum disulfide provided by the invention/reproducibility graphene oxide/nickel nano particle composite material, is aoxidized with reproducibility
Graphene is substrate, molybdenum disulfide nano sheet, nickel nano particle and reproducibility graphene oxide is carried out compound so that this is compound
Material has evolving hydrogen reaction catalytic activity simultaneously in acidic electrolysis bath and alkaline electrolyte, especially in alkaline electrolyte
Evolving hydrogen reaction catalytic activity is more preferable.Meanwhile preparation method provided by the invention, simple and practicable, raw material is cheap and easy to get, has fine
Economic prospect.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
The MoS that Fig. 1 is graphene oxide (a in Fig. 1), prepared by embodiment 12It is prepared by-rGO (b in Fig. 1), embodiment 2
MoS2MoS prepared by-rGO-Ni-30 (c in Fig. 1), embodiment 32MoS prepared by-rGO-Ni-50 (d in Fig. 1), embodiment 12-
The XRD diagram of Ni-rGO (f in Fig. 1) prepared by rGO-Ni-100 (e in Fig. 1), comparative example 1, unit：nm；
Fig. 2 is MoS prepared by embodiment 12- rGO and MoS2The XPS spectrum figure of-rGO-Ni-100, wherein (a)-(b) in Fig. 2
MoS is indicated successively2The Mo 3d spectrograms and S 2p spectrograms of-rGO；(d)-(f) indicates MoS successively2The Mo 3d spectrums of-rGO-Ni-100
Figure, S 2p spectrograms and Ni 2p spectrograms；(c) it is MoS2- rGO (i) and MoS2The full spectrum of-rGO-Ni-100 (ii)；
Fig. 3 is MoS prepared by embodiment 12- rGO (in Fig. 3 (a)) and MoS2The SEM of-rGO-Ni-100 (in Fig. 3 (b)) shines
Piece；
Fig. 4 indicates MoS prepared by embodiment 12The electrocatalysis characteristic test result of-rGO-Ni-100, wherein (a) is Ni-
RGO and MoS2- rGO-Ni-100 is in 0.5M H2SO4In evolving hydrogen reaction polarization curve, (b) be MoS2- rGO and MoS2-rGO-
Evolving hydrogen reaction polarization curves of the Ni-100 in 1M KOH, RHE indicate reversible hydrogen electrode.
Specific implementation mode
Molybdenum disulfide is one kind of transient metal sulfide, is stratified material.Recent study finds that molybdenum disulfide has
Evolving hydrogen reaction catalytic activity, active site derive from edge unsaturation sulphur atom.And nanometer class molybdenum disulfide can be carried significantly
High catalytic activity, usually, catalytic activity of hydrogen evolution of the molybdenum disulfide in acid medium are preferable.However, the conduction of molybdenum disulfide
Property is poor, can limit catalytic efficiency.
Reproducibility graphene oxide is because with higher electric conductivity, big specific surface area, flexibility and chemical stability etc.
Molybdenum disulfide nano sheet and nickel nano particle are creatively combined with each other by advantage, inventor with reproducibility graphene oxide,
On the one hand the electric conductivity that can increase composite material, on the other hand can reduce the reunion of nano particle, fully expose nano-particle
Active site, to obtain in acidic electrolysis bath and alkaline electrolyte while have the composite wood of evolving hydrogen reaction catalytic activity
Material.
Based on this, the present invention provides a kind of molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material,
, using reproducibility graphene oxide as substrate, molybdenum disulfide is scattered in nanometer sheet form in reproducibility graphene oxide substrate for it,
Nickel nano particle is dispersed on reproducibility graphene oxide substrate and molybdenum disulfide nano sheet.
Since molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material prepared by the present invention is anti-to liberation of hydrogen
There should be good catalytic action therefore can be used as evolving hydrogen reaction catalyst.
Further, inventor has found, molybdenum disulfide provided by the invention/reproducibility graphene oxide/nickel nano particle
When composite material is as evolving hydrogen reaction catalyst, the evolving hydrogen reaction catalytic activity in alkaline electrolyte is better than acid medium
In evolving hydrogen reaction catalytic activity；Therefore, in certain specific embodiments of the invention, the molybdenum disulfide/reproducibility oxygen
Graphite alkene/nickel nano particle composite material is in alkaline electrolyte as the evolving hydrogen reaction catalyst of electrolysis water.
But those skilled in the art know, nano-particle is easier to reunite, it is difficult to control its size and dispersibility.And
In the presence of sulphur source, nickel simple substance, which is easily combined with element sulphur, generates nickel sulfide, to cannot get nickel simple substance.
Hydro-thermal reaction is creatively combined with chemical reduction reaction by many experiments, first passes through hydro-thermal by inventor
Reaction realizes that molybdenum disulfide and reproducibility graphene oxide are compound, obtains molybdenum disulfide/reproducibility graphene oxide composite material,
While being re-introduced into nickel source, and nickel source is reduced into simple substance nickel nano particle by chemical reduction reaction, by elemental nickel nanoparticle
Son success is compound with molybdenum disulfide, reproducibility graphene oxide, finally obtains molybdenum disulfide/reproducibility graphene oxide/nickel and receives
Rice corpuscles composite material, while having obtained simple substance nickel nano particle, it is ensured that nickel nano particle is preferably dispersed.
Herein, reproducibility graphene oxide has the general sense of this field, refers to passing through graphene oxide also
Product obtained from former agent reduction, abbreviation rGO.In the present invention, it after graphene oxide being restored by hydro-thermal reaction, is gone back
Originality graphene oxide.
Based on above-mentioned mentality of designing, the present invention provides a kind of molybdenum disulfide/reproducibility graphene oxide/nickel nanoparticles
The preparation method of sub- composite material, including：
(1), graphene oxide is dispersed in water, obtains graphene oxide dispersion；
(2), molybdenum source, sulphur source are mixed with graphene oxide dispersion, obtains the first reaction mixture；
(3), first reaction mixture is divided after reaction hydro-thermal reaction 18-30 hours at 180 DEG C -220 DEG C
From, washing, obtain molybdenum disulfide/reproducibility graphene oxide composite material；
(4), the molybdenum disulfide/reproducibility graphene oxide composite material is scattered in organic solvent, obtains two sulphur
Change molybdenum/reproducibility graphene oxide composite material dispersion liquid；
(5), nickel source and hydrazine hydrate are added into the molybdenum disulfide/reproducibility graphene oxide composite material dispersion liquid
Afterwards, pH value is adjusted to 8-10, obtains the second reaction mixture；
(6), second reaction mixture is reacted 0.5-3 hours at 50-70 DEG C, detaches, washs after reaction,
Obtain molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material.
Graphene oxide of the present invention can be prepared by the prior art, and the present invention is at this to preparation method
Without limiting.
In specific implementation process, step (1) can be ultrasonically treated after mixing graphene oxide with water, with
Allow graphene oxide being dispersed in water faster, evenly, the time of supersound process can be 10-30 minutes；Aoxidize stone
The ratio of black alkene and water does not have particular/special requirement, as long as ensureing that graphene oxide can be adequately dispersed in water；It also wants simultaneously
Consider the volume of reaction kettle.Usually, the ratio of the volume of the quality and water of graphene oxide is 1：(1-2)mg/mL.
Molybdenum source and sulphur source used by technical scheme of the present invention are that can be dissolved in the molybdenum source and sulphur source of water, such as can be with
For water-soluble molybdenum salt and sulfosalt (sulfide)；In certain specific embodiments of the invention, the molybdenum source be selected from sodium molybdate,
One kind in ammonium molybdate or combinations thereof.In certain specific embodiments of the invention, sulphur source is in thiocarbamide, thioacetamide
One kind or combinations thereof.Sulphur source of the present invention is the sulphur source with reproducibility, can be used as reducing agent, pass through hydro-thermal
Graphene oxide is reduced into reproducibility graphene oxide by reaction.
In certain specific embodiments of the invention, since sulphur, the molybdenum atom ratio in molybdenum disulfide are 2：1, therefore,
In preparation process, the molar ratio of sulphur source and molybdenum source is generally higher than 2：1；Bigger ratio is conducive to the positive of reaction and carries out；It is preferred that
The molar ratio of ground, sulphur source and molybdenum source is (2.5-10)：1；The molal quantity of molybdenum source and the ratio of graphite oxide quality are (0.033-
0.1):1mol/g。
The hydro-thermal reaction of step (3) can be realized in water heating kettle.In specific implementation process, the first reaction mixture
Volume can be water heating kettle volume 60-90%.
It should be noted that the operating procedure of hydro-thermal reaction is well-known to those skilled in the art, existed according to the present invention
This related hydro-thermal reaction parameter, such as the temperature of hydro-thermal reaction, time etc. for providing, those skilled in the art need not pay wound
The hydro-thermal reaction of the present invention can be realized in the property made labour.
In certain specific embodiments of the invention, after the hydro-thermal reaction of step (3), centrifugation point can be carried out
From and separating obtained solid water and ethyl alcohol alternately being washed, until cleaning solution is colourless, and pH is about neutrality；After drying
To molybdenum disulfide/reproducibility graphene oxide composite material；Certainly, in addition to ethyl alcohol, acetone etc. can also be used volatile, less toxic
Organic solvent replace the ethyl alcohol to wash separating obtained solid.
In certain specific embodiments of the invention, the organic solvent in step (4) is one kind in ethylene glycol, ethyl alcohol
Or combinations thereof.In the specific implementation process of step (4), can by molybdenum disulfide/reproducibility graphene oxide composite material with
Organic solvent mix, be then ultrasonically treated so that molybdenum disulfide/reproducibility graphene oxide composite material can faster,
The time of being scattered in organic solvent evenly, supersound process can be 10-30 minutes；Molybdenum disulfide/reproducibility aoxidizes stone
The ratio of black alkene composite material and organic solvent does not have particular/special requirement, as long as ensureing that molybdenum disulfide/reproducibility graphene oxide is multiple
Condensation material can be adequately scattered in organic solvent；Usually, molybdenum disulfide/reproducibility graphene oxide composite material
The ratio of quality and the volume of organic solvent is 1：(1-2)mg/mL.
After obtaining molybdenum disulfide/reproducibility graphene oxide composite material dispersion liquid, nickel source and hydration are added thereto
Hydrazine, and its pH value is adjusted to 8-10, it is preferable that under stiring, such as under magnetic agitation, nickel source and hydrazine hydrate is added and adjusts pH
Value may make each substance dispersion evenly, to obtain uniform second reaction mixture in this way.
In step (5) specific implementation process, nickel source can selected from nickel sulfate, nickel nitrate, nickel chloride one kind or its
Combination.In some embodiments, the molal quantity of nickel source and the quality of molybdenum disulfide/reproducibility graphene oxide composite material
Ratio is (0.0018-0.007)：1mol/g.
The hydrazine hydrate being added in step (5) is as reducing agent, since commercially available hydrazine hydrate is usually that percent by volume is
The hydrazine hydrate aqueous solution of 40-80%, therefore when actually feeding intake, it can be according to the volume of determining pure hydrazine hydrate, by simple
Calculating determine the volume of the practical hydrazine hydrate aqueous solution to be added.
In certain specific embodiments of the invention, volume and the molybdenum disulfide/reproducibility graphite oxide of pure hydrazine hydrate
The ratio of the quality of alkene composite material is (0.02-0.03)：1mL/mg.
In step (5), pH value can be adjusted by the way that 1M KOH aqueous solutions are added, certain those skilled in the art also may be used
To be adjusted using the KOH or NaOH of other concentration；By adjusting pH value, make hydrazine hydrate that there is stronger reproducibility.
After obtaining the second reaction mixture, can by second reaction mixture at 50-70 DEG C reduction reaction
It 0.5-3 hours, after reaction, preferably waits for that temperature is cooled to room temperature, is detached, washed, obtain molybdenum disulfide/reproducibility oxygen
Graphite alkene/nickel nano particle composite material.It after the reduction reaction of step (6), can be centrifuged, and will divide
Molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material crude product from gained with ethyl alcohol wash for several times, until
Cleaning solution is colourless, and pH is about neutrality.Molybdenum disulfide/reproducibility graphene oxide composite material is obtained after drying；Certainly, in addition to
Ethyl alcohol, organic solvent that can also be volatile, less toxic using acetone etc. wash separating obtained crude product.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
First, the preparation method of graphene oxide (GO) is illustrated.Graphene oxide employed in the present invention can
To be prepared by improved Hummer methods, detailed process includes：
Weigh 2.5g graphite powders, 2.5g NaNO3, the dense H of 115mL are added2SO4, it is placed in ice-water bath, slowly adds while stirring
Enter 15g KMnO4.After about 40min, ice-water bath is removed, is put into 35 DEG C of water-baths, is slowly added to 230mL distilled water, this process
About 30min, product graduate into brown by black.It is put in later in 98 DEG C of oil baths and keeps the temperature 15min.After withdrawing from oil bath, it is added
50mL H are added in 700mL warm water (50-60 DEG C), stirring2O2, at this time product become golden yellow.Filtering is 5% with mass fraction
Dilute hydrochloric acid solution washing, then be washed with distilled water for several times, until with Ba (NO3)2It checks without SO4 2-Until.Products therefrom is in 70
DEG C air drying.
Molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material prepares embodiment
Embodiment 1
It weighs 30mg graphene oxides, 45mL redistilled waters (general deionized water can also), ultrasonic disperse is added
10 minutes, obtain graphene oxide dispersion.
Graphene oxide dispersion is transferred in 50mL reaction kettles, 0.4g (1.7mmol) Na is added2MoO4·2H2O and
0.63g (8.3mmol) thiocarbamide stirs 10min, obtains the first reaction mixture.
By the first reaction mixture at 200 DEG C hydro-thermal reaction 24 hours.The system of waiting for is cooled to room temperature, centrifugation, with water and
Ethyl alcohol alternately washs each 3 times, and products therefrom obtains molybdenum disulfide/reproducibility graphene oxide composite wood in 50 DEG C of vacuum drying
Material, abbreviation MoS2-rGO。
Weigh 16mg MoS220mL ethylene glycol is added in-rGO, and ultrasound is uniformly dispersed for 10 minutes, obtains molybdenum disulfide/reduction
Property graphene oxide composite material dispersion liquid.
Under magnetic stirring, 100 μ L 1M are added to molybdenum disulfide/reproducibility graphene oxide composite material dispersion liquid
NiCl2·6H2O ethylene glycol solutions (0.1mmol) and 0.5mL hydrazine hydrate aqueous solutions (concentration 80%), and 1mL 1M KOH water is added
Solution regulation system pH to 9 obtains the second reaction mixture.
Second reaction mixture is reacted 1 hour at 60 DEG C.After reaction, it waits for that system is down to room temperature, centrifuges, use second
Alcohol washs 3 times, and it is compound to obtain molybdenum disulfide/reproducibility graphene oxide/nickel nano particle in 50 DEG C of vacuum drying for products therefrom
Material, referred to as MoS2-rGO-Ni-100。
Embodiment 2
Embodiment 2 and embodiment 1 difference lies in：By 1M NiCl2·6H2The dosage of O ethylene glycol solutions is changed to 30 μ L, institute
Obtain molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, referred to as MoS2-rGO-Ni-30。
Embodiment 3
Embodiment 3 and embodiment 1 difference lies in：By 1M NiCl2·6H2The dosage of O ethylene glycol solutions is changed to 50 μ L, institute
Obtain molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, referred to as MoS2-rGO-Ni-50。
Embodiment 4
Embodiment 4 and embodiment 1 difference lies in：The temperature of hydro-thermal reaction is 180 DEG C, and the reaction time is 30 hours.
Embodiment 5
Embodiment 5 and embodiment 1 difference lies in：The temperature of hydro-thermal reaction is 220 DEG C, and the reaction time is 18 hours.
Embodiment 6
Embodiment 6 and embodiment 1 difference lies in：Sulphur source is thioacetamide；Molybdenum source is ammonium molybdate；Nickel source is sulfuric acid
Nickel.
Embodiment 7
Embodiment 7 and embodiment 1 difference lies in：The molal quantity of thiocarbamide is 17mmol.
Embodiment 8
Embodiment 8 and embodiment 1 difference lies in：Na2MoO4·2H2The molal quantity of O is 1mmol.
Embodiment 9
Embodiment 9 and embodiment 1 difference lies in：Na2MoO4·2H2The molal quantity of O is 3mmol.
The preparation of 1 nickel nano particle of comparative example/reproducibility graphene oxide composite material (Ni-rGO)
The synthetic method of Ni-rGO is as follows：20mg graphite oxides are dispersed in 30mL n-methyl-2-pyrrolidone, are surpassed
Sound disperses 3h, and 0.2695g (1mmol) nickel acetylacetonate, 2g (7mmol) octadecylamines and 1g KOH are added into dispersion liquid
(18mmol), then 4mL N are added dropwise2H4·H2O leads to 5min argon gas.Solution is transferred in 40mL reaction kettles, 180 DEG C of reactions
2h.After the completion of reaction, product n-hexane and acetone are alternately washed three times, then alternately washed twice with water and ethyl alcohol, product
It is dry in 40 DEG C of baking ovens.
The characterization of composite material and test
1, XRD analysis
X-ray powder diffraction instrument (the model produced using company of Dutch Panaco company：X Pert PRO MPD) to this
MoS prepared by inventive embodiments 12Composite material MoS prepared by-rGO and embodiment 1-32-rGO-Ni-100、MoS2-rGO-Ni-
30、MoS2- rGO-Ni-50 and GO and Ni-rGO carries out X-ray diffraction analysis, and analysis result is as shown in Figure 1；Analytic process
In radioactive source be Cu-Ka, measure step-length be 0.017 °, sweep time be 10 seconds/step.
From figure 1 it appears that a diffraction maximum occurs at d=0.84nm in GO (a in Fig. 1), corresponding interlamellar spacing is
0.84nm。MoS2There are two peaks at d=0.99nm and d=0.48nm in-rGO (b in Fig. 1), illustrates that interlamellar spacing is 0.99nm.
Normal MoS2Interlamellar spacing is 0.61nm, MoS2MoS in-rGO2The expansion of interlamellar spacing may be due to the intercalation of O elements.24 ° or so
Peak be rGO the peaks C, remaining peak is attributed to MoS2(PDF 65-1951), peak type is sharp, and crystallinity is high.
After nickel salt reaction is added, three species complex MoS of formation2- rGO-Ni-30 (c in Fig. 1), MoS2-rGO-Ni-50
(d in Fig. 1) and MoS2The XRD peak shapes of-rGO-Ni-100 (e in Fig. 1) are close, and interlamellar spacing can be observed and be expanded to 0.99nm's
MoS2Series diffractive peak and rGO the peaks C.In addition, the diffraction maximum of cubic phase Ni (PDF 65-0380) also can be observed, it was demonstrated that
MoS2The success of-rGO and Ni is compound.
Occur three diffraction maximums in the XRD spectra (f in Fig. 1) of Ni-rGO prepared by comparative example 1, with cubic phase Ni (PDF
65-0380) it is consistent.In addition the diffraction maximum that GO is not observed at d=0.84nm illustrates that GO is successfully restored.
2, XPS (x-ray photoelectron spectroscopy) is analyzed
X-ray photoelectron spectroscopy (the model produced using ThermoFisher companies of Britain：ESCSLAB250Xi) right
MoS prepared by embodiment 12- rGO and MoS2- rGO-Ni-100 carries out XPS analysis, using AlKl rays as x-ray source.XPS
Spectrogram is as shown in Figure 2；
Fig. 2 is MoS2- rGO and MoS2The XPS of-rGO-Ni-100 schemes.Spectrum (c) can be seen that entirely from Fig. 2, MoS2In-rGO
There are the elements such as Mo, S, C, O.In Fig. 2 (a), MoS2Mo in-rGO is mainly with Mo4+In the presence of (in conjunction with can 232.2eV and
228.9eV), also there is a small amount of Mo5+(in conjunction with energy 233.7eV) and Mo6+(in conjunction with energy 235.8eV), may be due to Mo4+Part
Oxidation.In Fig. 2 (b), S elements are mainly with S2-(in conjunction with energy 163.0eV and 161.8eV) and S2 2-(in conjunction with can 164.0eV and
162.0eV) two kinds of forms exist, and also have small part S to be oxidized to SO4 2-(in conjunction with energy 169.2eV).For MoS2-rGO-Ni-
100, full spectrum analysis shows in sample in addition to Mo, S, C, O element, also element containing Ni.In Fig. 2 (d), MoS2-rGO-Ni-100
The existence form of middle Mo does not change compared with precursor, and the content of high-valence state Mo increased.(e) is MoS in Fig. 22-
The combination energy of the S 2p of rGO-Ni-100 equally contains S in sample2-、S2 2-And SO4 2-, wherein SO4 2-Relative quantity also risen,
Illustrate that the degree of oxidation of sample surfaces increases.It is Ni0 in conjunction with that can be the peak of 852.7eV in Fig. 2 (f), and combination can be
Peak at 874.0eV, 870.0eV, 861.7eV and 856.1eV belongs to Ni2+, it was demonstrated that the presence of simple substance Ni.Ni is easy in air
It is aoxidized, therefore sample surfaces Ni containing part2+。
3, electron microscope analysis
The MoS using scanning electron microscope (SEM) prepared by embodiment 12- rGO and MoS2The pattern of-rGO-Ni-100
It is analyzed, the results are shown in Figure 3.
Fig. 3 is MoS2- rGO and MoS2The SEM results of-rGO-Ni-100.The MoS of (a) in Fig. 32- rGO electromicroscopic photographs,
RGO substrate surfaces grown many flower-like nanometer pieces, and nanometer sheet thickness is relatively thin, length dimension about 200-300nm, and surface is smooth.
The MoS of (b) in Fig. 32Many nickel simple substance nanoparticles have been interspersed in-rGO-Ni-100 electron microscopes, nanometer sheet surface and rGO substrates
Son, grain size become coarse on 10-20nm, nanometer sheet surface, and thickness increases.
4, electrocatalysis characteristic is tested
The MoS prepared with embodiment 12- rGO-Ni-100 samples carry out its electrocatalytic hydrogen evolution performance as catalyst
Test, and the MoS prepared with embodiment 12Ni-rGO prepared by-rGO (under alkaline condition) and comparative example 1 is (in acid condition
Under) as a comparison.Test uses standard three electrode system, and working electrode is glass-carbon electrode, is platinum electrode, reference electrode to electrode
For saturated calomel electrode.Catalyst loadings 0.56mg/cm2.Electrolyte is 0.5M H2SO4Or 1M KOH.To electrolysis before test
Lead to argon gas 30min in liquid to remove dissolved oxygen.Polarization curve is tested using linear sweep voltammetry, sweeps fast 2mV/s.As a result as schemed
Shown in 4.Electrolyte is 0.5M H2SO4When such as Fig. 4 in (a), MoS2- rGO-Ni-100 current densities reach 10mA/cm2It is required
Overpotential (η10) it is 325mV, with the increase of applied voltage, current density is further up.And MoS is not contained2Ni-
RGO comparative samples, η10For 428mV, illustrate MoS2Introducing can effectively improve the catalytic activity of composite material acid condition.This
Outside, MoS2- rGO-Ni-100 composite materials have more preferably catalytic activity, η in alkaline (1M KOH) (in such as Fig. 4 (b))10For
244mV, and comparative sample MoS2The η of-rGO10For 425mV, illustrate that the introducing of Ni significantly improves the catalytic activity of alkaline condition.
It should be noted that molybdenum disulfide/reproducibility graphene oxide/nickel nano particle prepared by embodiment 2-9
Characterization result and the result of embodiment 1 are substantially coincident, can also prove to have prepared molybdenum disulfide/reproducibility graphite oxide
Alkene/nickel nano particle composite material；Meanwhile the molybdenum disulfide prepared by embodiment 2-9/reproducibility graphene oxide/nickel nanometer
Particle also has the performance substantially consistent with the composite material of embodiment 1, may be used as evolving hydrogen reaction catalyst.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (10)
1. molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material, which is characterized in that aoxidize stone with reproducibility
Black alkene is substrate, and molybdenum disulfide nano sheet is scattered in reproducibility graphene oxide substrate, and nickel nano particle is dispersed in reproducibility
In graphene oxide substrate and molybdenum disulfide nano sheet.
2. the preparation method of molybdenum disulfide described in claim 1/reproducibility graphene oxide/nickel nano particle composite material,
It is characterised in that it includes：
(1), graphene oxide is dispersed in water, obtains graphene oxide dispersion；
(2), molybdenum source, sulphur source are mixed with graphene oxide dispersion, obtains the first reaction mixture；
(3), by first reaction mixture hydro-thermal reaction 18-30 hours at 180 DEG C -220 DEG C, detach after reaction,
Washing, obtains molybdenum disulfide/reproducibility graphene oxide composite material；
(4), the molybdenum disulfide/reproducibility graphene oxide composite material is scattered in organic solvent, obtain molybdenum disulfide/
Reproducibility graphene oxide composite material dispersion liquid；
(5), it after nickel source and hydrazine hydrate being added into the molybdenum disulfide/reproducibility graphene oxide composite material dispersion liquid, adjusts
Section pH value is 8-10, obtains the second reaction mixture；
(6), second reaction mixture is reacted 0.5-3 hours at 50-70 DEG C, detaches, washs after reaction, obtains
Molybdenum disulfide/reproducibility graphene oxide/nickel nano particle composite material.
3. preparation method as claimed in claim 2, which is characterized in that the molar ratio of sulphur source and molybdenum source is (2.5-10)：1；Molybdenum
The molal quantity in source and the ratio of graphite oxide quality are (0.033-0.1):1mol/g.
4. preparation method as claimed in claim 2, which is characterized in that the one kind of the molybdenum source in sodium molybdate, ammonium molybdate
Or combinations thereof；The one kind or combinations thereof of the sulphur source in thiocarbamide, thioacetamide.
5. preparation method as claimed in claim 2, which is characterized in that the nickel source is in nickel sulfate, nickel nitrate, nickel chloride
One kind or combinations thereof.
6. preparation method as claimed in claim 2, which is characterized in that the molal quantity of nickel source is aoxidized with molybdenum disulfide/reproducibility
The ratio of the quality of graphene composite material is (0.0018-0.007)：1mol/g.
7. preparation method as claimed in claim 2, which is characterized in that the volume of hydrazine hydrate is aoxidized with molybdenum disulfide/reproducibility
The ratio of the quality of graphene composite material is (0.02-0.03)：1mL/mg.
8. the preparation method as described in any one of claim 2-7, which is characterized in that the organic solvent is ethylene glycol, second
One kind in alcohol or combinations thereof.
9. molybdenum disulfide as described in claim 1/reproducibility graphene oxide/nickel nano particle composite material is anti-as liberation of hydrogen
Answer the purposes of catalyst.
10. purposes as claimed in claim 9, wherein the molybdenum disulfide/reproducibility graphene oxide/nickel nano particle is compound
Material is used as evolving hydrogen reaction catalyst in alkaline electrolyte.
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| CN112010291A (en) * | 2020-09-03 | 2020-12-01 | 郑州工程技术学院 | Preparation method and application of nickel-doped molybdenum disulfide/graphene three-dimensional composite material |
| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
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| CN111701596B (en) * | 2020-05-18 | 2023-02-17 | 天津大学 | Preparation method of atomic-scale active site catalyst for synthesizing ammonia under mild condition |
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| CN112903761A (en) * | 2021-01-19 | 2021-06-04 | 重庆大学 | Molybdenum disulfide-reduced graphene oxide-cuprous oxide ternary composite material and preparation method and application thereof |
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