CN104091936B - A kind of MoS2nanometer watt/graphene composite nano material and preparation method thereof - Google Patents
A kind of MoS2nanometer watt/graphene composite nano material and preparation method thereof Download PDFInfo
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- CN104091936B CN104091936B CN201410339878.8A CN201410339878A CN104091936B CN 104091936 B CN104091936 B CN 104091936B CN 201410339878 A CN201410339878 A CN 201410339878A CN 104091936 B CN104091936 B CN 104091936B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 80
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 59
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 59
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 20
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000012265 solid product Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 230000005518 electrochemistry Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of MoS2Nanometer watt/graphene composite nano material and preparation method, this composite nano materials is by the MoS of the layer structure of few number of plies2Nanometer watt is compound with Graphene to be constituted, MoS2The number of plies of nanometer watt mainly at 36 layers, MoS2And the ratio of the amount of the material between Graphene is 1:1 1:4.Its preparation method is first by graphene oxide ultrasonic disperse in deionized water, add Gemini surface active agent, and be sufficiently stirred for, then it is sequentially added into L cysteine and sodium molybdate, and is sufficiently stirred for making it dissolve, above-mentioned mixed dispersion is transferred in hydrothermal reaction kettle, at 230 250 DEG C after hydro-thermal reaction 20 24 h, naturally cooling to room temperature, centrifugal collection hydro-thermal solid product, through washing, dry, heat treatment acquisition.The method of the present invention has advantage simple, convenient, that be easily enlarged industrial applications.
Description
Technical field
The present invention relates to composite nano materials and preparation method thereof, particularly relate to MoS2Nanometer watt/Graphene composite Nano
Material and hydrothermal preparing process thereof, belong to inorganic composite nano field of material technology.
Background technology
Two-dimension nano materials has the characteristic of numerous excellence with the pattern of its uniqueness, and its research causes the most emerging of people
Interest.Graphene is most typical two-dimension nano materials, and the two-dimensional nano chip architecture of its uniqueness makes the physics of its numerous uniquenesses, chemistry
With performances such as mechanics, there is important scientific research meaning and technology application prospect widely.Graphene has high ratio table
Area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, the characteristic of these excellences makes graphite
Alkene is with a wide range of applications at aspects such as micro-nano electronic device, energy storage material and novel catalyst carriers.
The immense success that the discovery of Graphene and research thereof obtain excites people and grinds other inorganic two-dimension nano materials
The great interest studied carefully, such as monolayer or the transition metal dichalcogenide etc. of few number of plies.As a kind of typical case and important transition metal
Disulphide, MoS2Have with graphite-like as layer structure, be the S-Mo-S unit that combines of covalent bond in its layer, layer and layer it
Between combination be more weak Van der Waals force.This typical layered structure and weak Van der Waals force, make MoS2As kollag
There is relatively low friction factor, particularly still there is under the conditions of high temperature, fine vacuum etc. relatively low coefficient of friction, be a kind of excellent
Kollag.It addition, layer structure MoS2The embedding of external atom or ion, therefore MoS can be allowed2Stratiform chemical combination
Thing is also a kind of rising electrochemical lithium storage and storage Development of Magnesium Electrode Materials.
Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for
The inorganic material of layer structure, when its number of plies reduces (less than about 7 layers), when being especially reduced to monolayer, its electronic property or
Band structure can produce significantly change, thus causes which show the physics different from corresponding body phase material and chemical characteristic.
In addition to Graphene, recent research indicate that when body phase MoS2It is reduced to few number of plies (especially during monolayer), it is shown that with body phase material
Expect visibly different physics, chemistry and electronics property.Studies have reported that monolayer or the MoS of few number of plies2There is more preferable electrification
Learn storage lithium performance and high electrocatalytic hydrogen evolution reactivity.But storage lithium electrode material and the electro-catalysis material as electrochemical reaction
Material, MoS2The lowest electric conductivity have impact on its application performance.
Due to MoS2Nanometer sheet has similar two-dimensional nano sheet pattern with Graphene, and both tie at microscopic appearance and crystal
There is on structure good similarity.If by MoS2Nanometer sheet and Graphene are combined the composite of preparation, and Graphene is received
The high conduction performance of rice sheet can improve the electric conductivity of composite further, strengthens electrochemistry storage lithium and electrocatalytic reaction mistake
Electron transmission in journey, can improve electrochemistry storage lithium performance and the electrocatalysis characteristic of composite further.MoS2Nanometer sheet
The catalysis activity of electrocatalytic hydrogen evolution reaction be mainly derived from its active sites edge, increase MoS2The edge of nanometer sheet is to strengthen
One approach of electrocatalysis characteristic.It addition, as the MoS of electrochemistry storage lithium electrode material, more multiple edge2Nanometer sheet can provide
More and relatively short lithium ion diffusion admittance, contributes to booster electrochemistry storage lithium performance.With common MoS2Nanometer
Sheet compares, the MoS of little nanometer tiles pattern2Not only there is more edge, and it is supported on Graphene, with electrolyte
There is more contact area, its electrochemistry storage lithium performance can be strengthened.Therefore, this MoS2Being combined of nanometer watt/Graphene
The electrochemistry that nano material has a wide range of applications as electrochemistry storage lithium electrode material and evolving hydrogen reaction eelctro-catalyst and strengthens
Performance.
But, up to the present, MoS2Nanometer watt/graphene composite nano material and preparation thereof have not been reported.This
Bright with graphene oxide and sodium molybdate as raw material, the hydrothermal method assisted by Gemini surface active agent and heat treatment subsequently,
It is prepared for MoS2The composite nano materials of nanometer watt/Graphene.This preparation MoS2The composite nano materials of nanometer watt/Graphene
Method have simple, convenient and be easily enlarged industrial applications a little.
Summary of the invention
It is an object of the invention to provide a kind of MoS2Composite nano materials of nanometer watt/Graphene and preparation method thereof.
The technical scheme that the present invention solves the employing of its technical problem is as follows:
A kind of MoS2The composite nano materials of nanometer watt/Graphene, this composite nano materials is by MoS2Nanometer watt and Graphene
Compound composition, described MoS2Nanometer watt is the layer structure of few number of plies, MoS2The amount of the material between nanometer watt and Graphene it
Ratio is 1:1-1:4.
In technique scheme, the layer structure of few number of plies refers to that the number of plies is 6 layers or the layer structure of less than 6 layers.
As preferably, described MoS2The average number of plies of nanometer watt is 3-6 layer, MoS in composite nano materials2Nanometer watt and stone
The ratio of the amount of ink olefinic substance is 1:2.
MoS of the present invention2The composite nano materials of nanometer watt/Graphene, its preparation method is carried out as follows:
(1) Gemini surface active agent N-dodecyl by graphene oxide ultrasonic disperse in deionized water, it is subsequently adding
The trimethylene diamine double ammonium bromide schematic diagram of accompanying drawing 1 (its structure see), and be sufficiently stirred for；
(2) Cys and sodium molybdate are sequentially added in the mixed system of step (1), and are stirred continuously and make L-half Guang
Propylhomoserin and sodium molybdate are completely dissolved, and the ratio of the amount of the material of Cys and sodium molybdate consumption is 5:1, sodium molybdate and oxidation stone
The ratio of the amount of the material of ink alkene is 1:1-1:4；
(3) mixed dispersion that step (2) obtains is transferred in hydrothermal reaction kettle, and add deionized water adjustment body
Amass 80% to hydrothermal reaction kettle nominal volume, the concentration of the double ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine
Being 0.01 ~ 0.02 mol/L, the content of graphene oxide is 30-70mmol/L, puts in constant temperature oven by this reactor,
At 220-250 DEG C after hydro-thermal reaction 20-24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and spend
Ionized water fully washs, and is vacuum dried at 100 DEG C；By above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere
Heat treatment 2 h at 800 DEG C, in mixed gas, the volume fraction of hydrogen is 10%, obtains MoS2Being combined of nanometer watt/Graphene
Nano material.
Above-mentioned graphene oxide uses the Hummers method improved to prepare.
The hydrothermal method system assisted with the double ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine of the present invention
Standby MoS2The method of nanometer watt/graphene composite nano material has the advantage that surface of graphene oxide and edge are with very
Many oxygen-containing functional groups (such as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups make graphene oxide more easily be dispersed in water or have
In machine liquid, but these oxygen-containing functional groups make surface of graphene oxide with negative charge so that graphene oxide with negative
The MoO of electric charge4 2-Ion is incompatible, and the present invention passes through electrostatic interaction first by Gemini surface active agent N-dodecyl propylidene two
The double ammonium bromide of amine is adsorbed onto surface of graphene oxide so that it is with part positive charge, due to electrostatic interaction, MoO4 2-Ion is the most very
Easily interact with the graphene oxide having adsorbed Gemini surface active agent and combine.The more important thing is, with common
Single cationic surfactant is compared, and is just having 2 bands in the double ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine
The quaternary ammonium hydrophilic group of electricity, has between enough hydrophilic, and electronegative graphene oxide and has higher mutual electrostatic
Effect；The double ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine also has 2 hydrophobic long alkyl chain groups (its knot
Structure is as shown in Figure 1), its hydrophobicity is higher.The double ammonium bromide absorption of Gemini surface active agent N-dodecyl trimethylene diamine exists
Graphenic surface, there is (as shown in Figure 2) with irregular " brush head " form of bending in its hydrophobic group, this structure shape
Formula result in water-heat process and the heat treatment back loading MoS at graphenic surface2There is the pattern of nanometer watt, this undersized
MoS2Nanometer watt not only has more active sites edge, can strengthen its electrocatalysis characteristic to evolving hydrogen reaction, and permissible
The shortest lithium ion diffusion admittance is provided, contributes to strengthening its electrochemistry storage lithium performance.It addition, MoS2Nanometer watt/graphite
Alkene composite can increase the contact area of itself and electrolyte, further helps in and improves its chemical property.The present invention's
Method has feature that is simple, convenient and that be easily enlarged industrial applications.
Accompanying drawing explanation
The double ammonium bromide structural representation of Fig. 1 Gemini surface active agent N-dodecyl trimethylene diamine.
The absorption of Fig. 2 Gemini surface active agent is at the schematic diagram of surface of graphene oxide.
The MoS of Fig. 3 embodiment 12The XRD diffraction pattern of nanometer watt/graphene composite nano material.
The MoS of Fig. 4 embodiment 12The SEM shape appearance figure of nanometer watt/graphene composite nano material and transmission electron microscope photo.
The MoS of Fig. 5 comparative example 1 preparation2Nanometer sheet and the transmission electron microscope photo of graphene composite nano material.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.
Graphene oxide in following example uses the Hummers method improved to prepare: 0oUnder C ice bath, by 10.0
Mmol (0.12 g) graphite powder dispersed with stirring, in 50 mL concentrated sulphuric acids, is stirred continuously down and is slowly added into KMnO4, added KMnO4's
Quality is 4 times of graphite powder, stirs 50 minutes, when temperature rises to 35 DEG C, is slowly added into 50 mL deionized waters, is stirred for
30 minutes, add the H of 15 mL mass fractions 30%2O2, stir 30 minutes, through centrifugation, successively with mass fraction 5%
HCl solution, deionized water and acetone cyclic washing after obtain graphene oxide.
Embodiment 1
1) by 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, 0.8 mmol Shuangzi table is added
The double ammonium bromide of face activating agent N-dodecyl trimethylene diamine, and be sufficiently stirred for；
2) 0.76 g (6.25 mmol) Cys and 0.3 g (1.25mmol) sodium molybdate then it are sequentially added into
(Na2MoO42H2O), and it is stirred continuously and makes Cys and sodium molybdate be completely dissolved, adjust volume to about 80 with deionized water
mL；
3) transfer to obtained mixed liquor, in the hydrothermal reaction kettle of 100 mL, this reactor be put into constant temperature oven
In, at 230 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and use deionization
Water fully washs, and is vacuum dried at 100 DEG C；
4) by the solid product obtained by above-mentioned in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, gaseous mixture
In body, the volume fraction of hydrogen is 10%, prepares MoS2The composite nano materials of nanometer watt/Graphene, composite nano materials
Middle MoS2Nanometer watt is 1:2 with the ratio of the amount of Graphene material.
MoS is obtained to prepared by embodiment 1 with XRD, SEM and TEM2The composite nano materials of nanometer watt/Graphene is carried out
Characterizing, XRD analysis result (as shown in Figure 3) shows MoS in composite nano materials2For the layer structure of few number of plies, its average layer
Number is 4 layers.(see Fig. 4, wherein (a) is SEM shape appearance figure, and (b) and (c) is transmission electron microscope photo, (d) for SEM pattern and TEM photo
For high-resolution-ration transmission electric-lens photo) also clearly show the MoS being supported on Graphene2There is little nanometer shoe looks, MoS2
Nanometer watt has more uniform size, and its number of plies is 2-6 layer, and most numbers of plies are 4 layers, consistent with XRD analysis.
Comparative example 1
Use Dodecyl trimethyl ammonium chloride cationic surfactant, be prepared for MoS by above-mentioned similar approach2Nanometer
The composite nano materials of sheet/Graphene, concrete preparation process is as follows:
By 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, add 1.6 mmol dodecyls
Trimethylammonium bromide cationic surfactant, and be sufficiently stirred for, then it is sequentially added into 0.76g (6.25 mmol) L-half Guang ammonia
Acid and 0.3 g (1.25 mmol) sodium molybdate (Na2MoO42H2And be stirred continuously and make Cys and sodium molybdate the most molten O),
Solve, with deionized water adjustment volume to about 80 mL, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, will
This reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24 h, allows it naturally cool to room temperature, receives with centrifugation
Collection solid product, and fully wash with deionized water, it is vacuum dried at 100 DEG C, exists stating obtained hydro-thermal solid product
In nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2 h, in mixed gas, the volume fraction of hydrogen is 10%, prepares
MoS2The nano composite material of nanometer sheet/Graphene.
With XRD, SEM and TEM to finally preparing MoS2Nanometer sheet characterizes with the nano composite material of Graphene,
XRD analysis result shows MoS in composite nano materials2For layer structure, its average number of plies is 7 layers.TEM and HRTEM photo (see
Fig. 5, wherein (a) is transmission electron microscope photo, and (b) is high-resolution-ration transmission electric-lens photo) show the MoS being supported on Graphene2
Having the pattern of nanometer sheet, its number of plies is at 6-9 layer, MoS2Nanometer sheet size there is no above-mentioned MoS yet2Nanometer watt uniform.
Electrocatalytic reaction Hydrogen Evolution Performance is tested and compares: the MoS 4.0 mg embodiments 1 prepared2Nanometer watt/Graphene is multiple
Conjunction nano material (or the MoS of comparative example 1 preparation2Nanometer sheet/graphene composite nano material) add the deionized water of 1.0 mL-
In alcohol mixeding liquid body (volume ratio 1:1), add the Nafion solution (5 wt%) of 30 uL, supersound process 2 h so that it is fill
Point mixing is uniformly dispersed, and obtains uniform slurry, takes the mixed slurry of 5 uL with liquid-transfering gun and drips to the vitreous carbon electricity of diameter 5 mm
Extremely go up, after drying at 80 DEG C, obtain test job electrode.Electrolyte is the aqueous sulfuric acid of 0.5 M, and reference electrode is saturated sweet
Mercury electrode, platinized platinum is as to electrode, with linear sweep voltametry test material to evolving hydrogen reaction on CHI660B electrochemical workstation
Electrocatalysis characteristic test, scanning speed is 5 mV/s.Test result shows under identical cathodic polarization potential, MoS2
Electrode prepared by nanometer watt/graphene composite nano material compares MoS2Electrode prepared by nanometer sheet/graphene composite nano material
There is higher evolving hydrogen reaction electric current.As: under 0.20 V vs. RHE current potential, at MoS2Nanometer watt/Graphene composite Nano
On material electrodes, electrochemical catalysis evolving hydrogen reaction electric current is 16.5 mA, at MoS2Nanometer sheet/graphene composite nano material electrode
Upper evolving hydrogen reaction electric current is 6.6 mA.Enhancing to evolving hydrogen reaction electrocatalysis characteristic is due to MoS2Nanometer watt/Graphene is combined
The MoS that nano material is medium and small2Nanometer watt compares MoS2MoS in nanometer sheet/graphene composite nano material2Nanometer sheet has more
Active sites edge.It addition, MoS2Nanometer watt/graphene composite nano material compares MoS2Nanometer sheet/graphene composite nano material tool
There is more and electrolyte contacts area.
Embodiment 2
1) by 2.5 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, 0.8 mmol Shuangzi table is added
The double ammonium bromide of face activating agent N-dodecyl trimethylene diamine, and be sufficiently stirred for；
2) 1.50g (12.5 mmol) Cys and 0.6 g (2.5 mmol) sodium molybdate then it are sequentially added into
(Na2MoO42H2O), and it is stirred continuously and makes Cys and sodium molybdate be completely dissolved, adjust volume to about 80 with deionized water
mL；
3) transfer to obtained mixed liquor, in the hydrothermal reaction kettle of 100 mL, this reactor be put into constant temperature oven
In, at 220 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and use deionization
Water fully washs, and is vacuum dried at 100 DEG C；
4) by the solid product obtained by above-mentioned in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, be prepared into
To MoS2The composite nano materials of nanometer watt/Graphene, in mixed gas, the volume fraction of hydrogen is 10%.
Characterizing end product obtained after heat treatment with XRD, SEM and HRTEM, characterization result shows last gained
To product be MoS2The composite nano materials of nanometer watt/Graphene, MoS2The average number of plies of nanometer watt is 5 layers, wherein MoS2Nanometer
Watt with the ratio=1:1 of the amount of Graphene material.
Embodiment 3
1) by 3.75 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, 1.2 mmol Shuangzis are added
The double ammonium bromide of surfactant N-dodecyl trimethylene diamine, and be sufficiently stirred for；
2) 0.76g (6.25 mmol) Cys and 0.3 g (1.25 mmol) sodium molybdate then it are sequentially added into
(Na2MoO42H2O), and it is stirred continuously and makes Cys and sodium molybdate be completely dissolved, adjust volume to about 80 with deionized water
mL；
3) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water adjustment volume extremely
80 mL, put in constant temperature oven by this reactor, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with from
The heart separates and collects solid product, and fully washs with deionized water, is vacuum dried at 100 DEG C；
4) by the solid product obtained by above-mentioned in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, be prepared into
To MoS2The composite nano materials of nanometer watt/Graphene, in mixed gas, the volume fraction of hydrogen is 10%.
Characterizing end product obtained after heat treatment with XRD, SEM and HRTEM, characterization result shows last gained
It is MoS to product2Nanometer watt/graphene composite nano material, MoS2The average number of plies of nanometer watt is 3 layers, wherein MoS2With graphite
The ratio of the amount of olefinic substance is 1:3.
Embodiment 4
1) by 5.0 mmol graphene oxide ultrasonic disperse in 60 mL deionized waters, 1.6 mmol Shuangzi tables are added
The double ammonium bromide of face activating agent N-dodecyl trimethylene diamine, and be sufficiently stirred for；
2) 0.76g (6.25 mmol) Cys and 0.3 g (1.25 mmol) sodium molybdate then it are sequentially added into
(Na2MoO42H2O), and it is stirred continuously and makes Cys and sodium molybdate be completely dissolved, adjust volume to about 80 with deionized water
mL；
3) transfer to obtained mixed liquor, in the hydrothermal reaction kettle of 100 mL, this reactor be put into constant temperature oven
In, at 250 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and use deionization
Water fully washs, and is vacuum dried at 100 DEG C；
4) by the solid product obtained by above-mentioned in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, be prepared into
To MoS2The composite nano materials of nanometer watt/Graphene, in mixed gas, the volume fraction of hydrogen is 10%.
With XRD, SEM and HRTEM, end product obtained after heat treatment is characterized, after characterization result display heat treatment
Obtaining product is MoS2The composite nano materials of nanometer watt/Graphene, MoS2The average number of plies of nanometer watt is 3 layers, wherein MoS2With stone
Ratio=the 1:4 of the amount of ink olefinic substance.
Claims (2)
1. a MoS2The composite nano materials of nanometer watt/Graphene, it is characterised in that this composite nano materials is by MoS2Nanometer
Watt compound with Graphene constitute, described MoS2Nanometer watt is the layer structure of few number of plies, described MoS2Between nanometer watt and Graphene
The ratio of amount of material be 1:1-1:4, the preparation process of described composite nano materials is performed as follows:
(1) Gemini surface active agent N-dodecyl Asia third by graphene oxide ultrasonic disperse in deionized water, it is subsequently adding
The double ammonium bromide of base diamidogen, and be sufficiently stirred for；
(2) then Cys and sodium molybdate are added sequentially in the mixed system that step (1) obtains, and are stirred continuously and make
Cys and sodium molybdate are completely dissolved, and the ratio of the amount of the material of Cys and sodium molybdate consumption is 5:1, sodium molybdate with
The ratio of the amount of the material of graphene oxide is 1:1-1:4；
(3) mixed dispersion that step (2) obtains is transferred in hydrothermal reaction kettle, and add deionized water adjustment volume extremely
The 80% of hydrothermal reaction kettle nominal volume, the concentration of the double ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine is
0.01～0.02mol/L, the content of graphene oxide is 30-70mmol/L, puts in constant temperature oven by this reactor, at 220-
At 250 DEG C after hydro-thermal reaction 20-24h, allow it naturally cool to room temperature, collect hydro-thermal solid product with centrifugation, and spend
Ionized water fully washs, and is vacuum dried at 100 DEG C, by the hydro-thermal solid product that obtains in nitrogen/hydrogen mixed gas atmosphere in
Heat treatment 2h at 800 DEG C, in mixed gas, the volume fraction of hydrogen is 10%, finally prepares MoS2Nanometer watt/Graphene
Composite nano materials.
MoS the most according to claim 12The composite nano materials of nanometer watt/Graphene, it is characterised in that described MoS2Receive
The number of plies of rice watt is 3～6 layers.
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| CN106960948B (en) * | 2016-07-27 | 2020-07-10 | 北京大学 | MoSxCarbon black nano composite material, preparation method and application thereof |
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| CN111883753B (en) * | 2020-07-16 | 2021-11-09 | 上海鼎瀛信息科技有限公司 | MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere |
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