CN102698774B - Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material - Google Patents
Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material Download PDFInfo
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- CN102698774B CN102698774B CN201210187871.XA CN201210187871A CN102698774B CN 102698774 B CN102698774 B CN 102698774B CN 201210187871 A CN201210187871 A CN 201210187871A CN 102698774 B CN102698774 B CN 102698774B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002356 single layer Substances 0.000 title abstract description 9
- 229910052961 molybdenite Inorganic materials 0.000 title abstract 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title abstract 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 30
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 30
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000012265 solid product Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003093 cationic surfactant Substances 0.000 claims description 20
- 238000005119 centrifugation Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000003595 mist Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 3
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 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 2
- 239000004201 L-cysteine Substances 0.000 abstract 1
- 235000013878 L-cysteine Nutrition 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 57
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 11
- 239000003643 water by type Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 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
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention discloses a hydrothermal preparation method for single-layer MoS2 and a graphene composite nano material. The composite material is formed by compounding the single-layer MoS2 and graphene, wherein a molar ratio of the single-layer MoS2 to the graphene is (1:1)-(1:4). The preparation method comprises the following steps of: performing ultrasonic dispersion on graphene oxide in deionized water, stirring, adding a cation surfactant, and adding L-cysteine and sodium molybdate sequentially; transferring the mixed dispersed system into a hydrothermal reaction kettle, performing hydrothermal reaction at the temperature of between 220 and 250 DEG C for 24 hours, and cooling naturally; centrifuging and collecting a solid product, washing the product by using deionized water, drying, and performing heat treatment under mixed atmosphere of nitrogen/hydrogen. The method has the advantages of simplicity and convenience, and an organic solvent is not required.
Description
Technical field
The present invention relates to the preparation method of composite nano materials, relate in particular to individual layer MoS
2with the hydrothermal preparing process of graphene composite material, belong to inorganic composite nano material technology field.
Background technology
Recently, the research of individual layer two-dimensional nano material has caused people's very big interest.As everyone knows, Graphene is current maximum individual layer two-dimensional nano materials of research, and Graphene has the performances such as physics, chemistry and mechanics of numerous uniquenesses with its unique two-dimensional nano chip architecture, has important scientific research meaning and application prospect widely.Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property.Graphene is with a wide range of applications as the electrode material of micro-nano electronic device, new forms of energy battery, kollag and novel catalyst carrier.The discovery of Graphene and application study thereof have excited the research interest of people to other inorganic individual layer two-dimensional nano materials, as have the transition metal dichalcogenide MoS of single layer structure
2and WS
2.
MoS
2the typical layered structure with similar graphite.MoS
2layer structure is the layer structure of sandwich, and in its layer, (S-Mo-S) is very strong covalent bonds, and interlayer is weak Van der Waals force, easily peels off between layers.MoS
2there is good anisotropy and lower friction factor, MoS
2can be attached to well metal surface performance lubricating function, particularly under the conditions such as high temperature, high vacuum, still have lower coefficient of friction, be a kind of good kollag.MoS
2also be a kind of catalyst carrier of good catalytic desulfurization.The MoS with layer structure
2as material of main part, by insertion, react, object atom or molecule can be inserted in and between body layer, form intercalation compound.Due to MoS
2lamellar compound be by weak Van der Waals force combination between layers, therefore can allow at interlayer, to introduce external atom or molecule by intercalation.Therefore, MoS
2lamellar compound is a kind of up-and-coming electrochemical lithium storage and storage Development of Magnesium Electrode Materials.But as the electrode material of electrochemical reaction, MoS
2electric conductivity poor.
The inorganic compound of layer structure, but its number of plies is when less (5 layers are following), and its Electronic Performance and its number of plies have substantial connection.Research recently discloses to be compared with body phase material, the MoS of single layer structure
2and WS
2there are uncommon physical chemistry and photoelectric properties, as: the MoS of single layer structure
2raman spectrum have obvious variation and significantly strengthen fluorescence quantum efficiency, the MoS of single layer structure
2the transistor of preparation has high on-off ratio.The MoS of single layer structure
2as lithium ion battery negative material, also shown good performance.But due to MoS
2be semi-conducting material in essence, its electronic conductivity is not high enough, as the application of electrode material, need to strengthen its electric conductivity.
Due to individual layer MoS
2have similar two-dimensional nano sheet pattern with Graphene, both have good similitude on microscopic appearance and crystal structure.Individual layer MoS
2can apply as electrode material and catalyst with graphene nanometer sheet.If by individual layer MoS
2composite with the compound preparation of graphene nanometer sheet, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite, strengthen the electronics transmission in electrochemical electrode reaction and catalytic reaction process, can further improve chemical property and the catalytic performance of composite.Individual layer MoS in addition
2compound with graphene nanometer sheet, the large Π key of graphene nanometer sheet can with MoS
2the interaction of Electronic Structure, further strengthens the ability of electronics transmission and charge migration.Therefore, this individual layer MoS
2the performance that has a wide range of applications and strengthen as electrode material and catalyst carrier etc. with the composite nano materials of graphene nanometer sheet.
But, up to the present, individual layer MoS
2preparation be mainly the insertion based on lithium ion and the method peeled off, there is following shortcoming in this method: responsive to environment highs such as air, moisture, need to consume a large amount of organic solvents, time that need to be longer.From large-scale application, consider, research and develop a kind of individual layer MoS for preparing simply and easily
2with the method for graphene composite material be still a job with challenge and novelty.
The present invention adopts cationic surfactant, and graphene oxide and sodium molybdate are raw material, by hydro-thermal reaction easily, prepares individual layer MoS
2composite with Graphene.But so far, this method yet there are no open report.
Summary of the invention
The object of the present invention is to provide
oneplant individual layer MoS
2hydrothermal preparing process with graphene composite material.
Individual layer MoS
2with the hydrothermal preparing process of Graphene composite nano materials, this composite is by individual layer MoS
2with the compound formation of Graphene, individual layer MoS
2and the ratio of the amount between Graphene is 1:1-1:4, and its preparation process is as follows:
(1) be dispersed in deionized water graphene oxide is ultrasonic, then add cationic surfactant, and fully stir;
(2) Cys and sodium molybdate are added in the mixed system of step (1) successively, and constantly stir Cys and sodium molybdate are dissolved completely, the ratio of the amount of Cys and sodium molybdate consumption is 5:1, sodium molybdate with the ratio of the amount of graphene oxide at 1:1-1:4;
(3) mixed dispersion step (2) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, cationic surfactant concentration is 0.02-0.05 M, the content of graphene oxide is 31.25-62.5 mmol/L, this reactor is put in constant temperature oven, at 220-250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and by deionized water, fully wash vacuum drying at 100 ℃;
(4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer MoS
2composite nano materials with Graphene.
In the present invention, described cationic surfactant is softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide.
Above-mentioned graphene oxide can adopt improved Hummers method preparation.
Hydrothermal method with cationic surfactant assistance of the present invention is prepared individual layer MoS
2have the following advantages with the method for Graphene composite nano materials: graphene oxide surface and edge with a lot of oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups are more easily dispersed in water or organic liquid graphene oxide, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide with the MoS of negative electrical charge
4 2-ion is incompatible, and the present invention is first adsorbed onto cationic surfactant graphene oxide surface by electrostatic interaction, and make it with part positive charge, and then mix with ammonium thiomolybdate, due to electrostatic interaction, MoS
4 2-ion just easily interacts and combines with the graphene oxide that has adsorbed cationic surfactant, more just prepares individual layer MoS by hydro-thermal reaction and heat treatment subsequently
2with graphene composite material.Method of the present invention has technique feature simply and easily, does not consume organic solvent.
Accompanying drawing explanation
Fig. 1 is individual layer MoS
2the XRD diffraction pattern of/graphene composite material, in figure, * is individual layer MoS
2with individual layer MoS
2between interlamellar spacing, # is individual layer MoS
2and the interlamellar spacing between Graphene.
Curve (a) is the individual layer MoS of embodiment 1 preparation
2/ graphene composite material;
Curve (b) is the individual layer MoS of embodiment 3 preparations
2/ graphene composite material;
fig. 2the simple MoS preparing for comparative example
2xRD diffraction pattern;
fig. 3the individual layer MoS of embodiment 1 preparation
2/ graphene composite material SEM pattern;
fig. 4the individual layer MoS of embodiment 1 preparation
2/ graphene composite material HRTEM figure.
The specific embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Graphene oxide in following example adopts improved Hummers method preparation: 0
ounder C ice bath, 5.0-10.0 mmol (0.06-0.12 g) graphite powder dispersed with stirring, in the 30 mL concentrated sulfuric acids, is slowly added to KMnO under constantly stirring
4, institute adds KMnO
4quality be 4 times of graphite powder, stir 50 minutes, when temperature rises to 35 ℃, slowly add 50 ml deionized waters, then stir 30 minutes, add the H of 15 ml mass concentrations 30%
2o
2, stir 30 minutes, through centrifugation, successively with obtaining graphene oxide after mass concentration 5%HCl solution, deionized water and acetone cyclic washing.
Embodiment 1.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 1.6 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 240 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, its XRD is shown in Fig. 1 curve (a), SEM is shown in Fig. 3, HRTEM is shown in Fig. 4, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:2 with Graphene amount.
Comparative example, does not add cationic surfactant and graphene oxide in preparation process, by above-mentioned similar approach, prepared simple MoS
2, concrete preparation process is as follows:
In 60 mL deionized waters, add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely, resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 240 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃, by resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, prepare individual layer MoS
2with the composite nano materials of Graphene, its XRD diffraction pattern is shown in Fig. 2, and XRD characterizes and shows prepared simple MoS
2there is very strong (002) face XRD diffraction maximum, the simple MoS that surface is prepared
2for sandwich construction, its average number of plies is 21 layers.
Embodiment 2.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 2.4 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 230 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:2 with Graphene amount.
Embodiment 3.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 4.0 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, its XRD is shown in Fig. 1 curve (b), characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:2 with Graphene amount.
Embodiment 4.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 4.0 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 1.50g (12.38 mmol) Cys and 0.6 g (2.48 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:1 with Graphene amount.
Embodiment 5.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 4.0 mmol DTAB cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 245 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:2 with Graphene amount.
Embodiment 6.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 4.0 mmol eight alkyl trimethyl ammonium bromide cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 240 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:2 with Graphene amount.
Embodiment 7.
1) be dispersed in 60 mL deionized waters 3.75 mmol graphene oxides are ultrasonic, then add 3.2 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 235 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:3 with Graphene amount.
Embodiment 8.
1) be dispersed in 60 mL deionized waters 5.0 mmol graphene oxides are ultrasonic, then add 1.6 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:4 with Graphene amount.
Embodiment 9.
1) be dispersed in 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, then add 2.4 mmol tetra-n-butyl ammonium bromide cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.3 g (1.24 mmol) sodium molybdate (Na
2moO
42H
2o), and constantly stir Cys and sodium molybdate are dissolved completely;
3) resulting mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL, this reactor is put in constant temperature oven, at 250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and fully wash by deionized water, vacuum drying at 100 ℃;
4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, prepare individual layer MoS
2with the composite nano materials of Graphene, in mist, the volume ratio of hydrogen is 10%.
With XRD, SEM and HRTEM to heat treatment after resulting end product characterize, characterization result shows that obtaining product after heat treatment is individual layer MoS
2/ graphene composite material, wherein MoS
2ratio=1:2 with Graphene amount.
Claims (1)
1.
oneplant individual layer MoS
2with the hydrothermal preparing process of Graphene composite nano materials, this composite nano materials is by individual layer MoS
2with the compound formation of Graphene, individual layer MoS
2and the ratio of the amount of substance between Graphene is 1:1-1:4, and its preparation process is as follows:
(1) be dispersed in deionized water graphene oxide is ultrasonic, then add cationic surfactant, and fully stir, described cationic surfactant is softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide;
(2) Cys and sodium molybdate are added in the mixed system of step (1) successively, and constantly stir Cys and sodium molybdate are dissolved completely, the ratio of the amount of Cys and sodium molybdate consumption is 5:1, sodium molybdate with the ratio of the amount of graphene oxide at 1:1-1:4;
(3) mixed dispersion step (2) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, cationic surfactant concentration is 0.02-0.05 M, the content of graphene oxide is 31.25-62.5 mmol/L, this reactor is put in constant temperature oven, at 220-250 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation, collect solid product, and by deionized water, fully wash vacuum drying at 100 ℃;
(4) by above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer MoS
2composite nano materials with Graphene.
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