CN102142548B - Compound nano material of graphene and MoS2 and preparation method thereof - Google Patents
Compound nano material of graphene and MoS2 and preparation method thereof Download PDFInfo
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- CN102142548B CN102142548B CN201110046467.6A CN201110046467A CN102142548B CN 102142548 B CN102142548 B CN 102142548B CN 201110046467 A CN201110046467 A CN 201110046467A CN 102142548 B CN102142548 B CN 102142548B
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Abstract
The invention discloses a compound nano material of graphene and molybdenum disulfide (MoS2) and a preparation method thereof. The compound material is formed by mixing graphene and a MoS2 nano material in a mass ratio of (1 to 1)-(4 to 1). The preparation method comprises the following steps of: preparing an oxidized graphite nano slice from graphite by a chemical oxidization method; then dissolving molybdate into deionized water so as to form 0.02 to 0.07M of solution; adding L-cysteine serving as a sulfur source and a reduction agent, wherein the mass ratio of the L-cysteine to the molybdate is (5 to 1)-(12 to 1); adding the oxidized graphite nano slice into the solution, and ultrasonically treating so that the oxidized graphite nano slice can be fully dispersed in the hydrothermal reaction solution; transferring the mixture into a hydrothermal reaction kettle and sealing; and synthesizing by a one-step hydrothermal method to obtain the compound nano material of graphene and MoS2, wherein the mass ratio of the graphene nano slice to the MoS2 is (1 to 1)-(4 to 1). The method has the characteristics of mild reaction condition and simple process. The compound nano material of graphene and MoS2 synthesized by the method can be widely used as electrode materials of new energy batteries, high-performance national lubricants, catalyst carriers and the like.
Description
Technical field
The present invention relates to composite nano materials and preparation thereof, relate in particular to Graphene and MoS
2composite nano materials and preparation method thereof, belong to inorganic composite nano material, new energy materials and preparation field thereof.
Background technology
The graphene nanometer sheet two-dimensional nano chip architecture unique with it has the performances such as physics, chemistry and mechanics of numerous uniquenesses, has important scientific research meaning and application prospect widely.The finder of grapheme material obtains the Nobel Prize in 2010 and has excited especially the very big interest of people to grapheme material research.Graphene nanometer sheet has high specific area, high conduction and heat conductivility, superpower mechanical property.Recently people have carried out research widely to graphene nanometer sheet as the application of the electrode material of micro-nano electronic device, new forms of energy battery, kollag and novel catalyst carrier.
On the other hand, MoS
2typical layered structure with similar graphite.MoS
2the layer structure that layer structure is sandwich, be very strong covalent bond (S-Mo-S) in its layer, 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
2it is also a kind of catalyst carrier of good catalytic desulfurization.The MoS that there is in addition layer structure
2as material of main part, by insertion, react, object atom or molecule can be inserted between body layer and form intercalation compound.Due to MoS
2lamellar compound be by weak Van der Waals force combination between layers, therefore can allow to introduce external atom or molecule by intercalation at interlayer.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.
Due to graphene nanometer sheet and MoS
2there is typical layer structure, graphene nanometer sheet and MoS
2nanometer sheet is eventful is very promising electrode material and catalyst carrier.Therefore, if prepare graphene nanometer sheet/MoS
2composite nano materials, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite material, is conducive to the electronics transmission in electrochemical electrode reaction and catalytic reaction process, the chemical property of reinforced composite and catalytic performance.Graphene nanometer sheet and MoS in addition
2compound, due to large ∏ key and the MoS of graphene nanometer sheet
2the interaction of Electronic Structure, can form the electronic structure between a kind of new different material.This graphene nanometer sheet/MoS
2composite nano materials stores as electrochemistry the performance that lithium, electrochemistry storage magnesium and catalyst carrier etc. have a wide range of applications and improve.
The application of biological micromolecule in nano material is synthetic recently obtained people's extensive concern.Cys contains a plurality of functional group (as: NH
2,-COOH and-SH), these functional groups can provide coordination atom and metal cation to form coordinate bond.Cys has obtained application in synthetic transient metal sulfide nano material.Document [Zhang B, Ye XC, Hou WY, Zhao Y, Xie Y.Biomolecule-assistedsynthesis and electrochemical hydrogen storage of Bi
2s
3flowerlike patterns withwell-aligned nanorods.Journal of Physical Chemistry B, 2006,110 (18) 8978～8985] synthesized the Bi of floriform appearance with Cys
2s
3nano structural material.But up to the present, with containing Cys, assist synthesizing graphite alkene/MoS
2composite nano materials and preparation method thereof yet there are no open report.
Summary of the invention
The object of the present invention is to provide a kind of Graphene and MoS
2composite nano materials and preparation method thereof, it is characterized in that composite material is by Graphene and MoS
2the compound formation of nano material, Graphene and MoS
2between nano material, the ratio of amount is 1: 1-4: 1.
A kind of Graphene provided by the invention and MoS
2the preparation method of composite nano materials carry out as follows:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, the 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be graphite 3-4 doubly, stir 30-60 minute, temperature rises to 30-35 ℃ of left and right, adds the 40-50ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30%
2o
2, stir 5-20 minute, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) molybdate is dissolved in deionized water to the solution that forms 0.02～0.07M, adding Cys is sulphur source and reducing agent, Cys is 5: 1～12: 1 with the ratio of the amount of molybdate, again will be by the 1st) the preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) step graphite raw material amount of substance used is 1: 1～4: 1 with the ratio of the amount of molybdate, ultrasonic processing 1-2h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, this mixture is proceeded in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and seal, at 200-240 ℃ of reaction 20-36h, the product centrifugation obtained, and with deionized water and absolute ethanol washing, dry, finally at 90%N
2-10%H
2in atmosphere, 800-1000 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials.
Said molybdate is sodium molybdate or ammonium molybdate.
Method of the present invention has the simple characteristics that wait of the gentle preparation technology of reaction condition.Synthesizing graphite alkene of the present invention and MoS
2composite nano materials as the electrode material of new forms of energy battery lithium ion battery, electrochemistry storage Development of Magnesium Electrode Materials, kollag and catalyst carrier, have a wide range of applications.
Method of the present invention has advantages of following outstanding compared with the prior art:
(1) because graphene nanometer sheet has the excellent properties such as high specific area, superpower mechanical property, high conduction and heat conduction, therefore, Graphene of the present invention and MoS
2composite nano materials there is mechanical property, conduction and the heat conductivility of enhancing, be conducive to it as the electrode reaction of new forms of energy battery electrode material, electronics transmission in catalytic reaction process, strengthen chemical property and the catalytic performance of composite nano materials.And the superpower mechanical property of graphene nanometer sheet has also strengthened the mechanical property of composite nano materials, can improve its tribological property as kollag.Graphene nanometer sheet and MoS in addition
2compound, due to large ∏ key and the MoS of graphene nanometer sheet
2the interaction of Electronic Structure, can form the electronic structure between a kind of new different material, and the electrons height delocalization of participation role, be conducive to the quick transmission of electronics in electrochemical reaction process.This Graphene and MoS
2composite nano materials have a wide range of applications and strengthen the performance of improvement as electrode material electrochemistry storage lithium, electrochemistry storage magnesium and catalyst carrier etc.
(2) the present invention's stannic oxide/graphene nano sheet, and soluble molybdenum hydrochlorate, Cys are raw material, adopt the Situ Hydrothermal reducing process to become out Graphene and MoS
2composite nano materials.Synthetic method of the present invention has the reaction condition gentleness, and technique is simple, the advantage of the high and favorable reproducibility of productive rate.
(3) in course of reaction of the present invention, stannic oxide/graphene nano sheet in-situ reducing becomes graphene nanometer sheet, and reacts the molybdenum disulfide nano Material cladding formation composite material formed with Situ Hydrothermal.Its advantage is: the graphite oxide nanometer sheet contains abundant oxygen-containing functional group (as: hydroxyl, carbonyl and carboxyl etc.), no longer easily again reunited later or be deposited in together by ultrasonic dispersion in hydro-thermal reaction solution, and the functional group on graphite oxide surface can be adsorbed on molybdate the surface of graphite oxide nanometer sheet by complexing, in the reproducibility hydrothermal reaction process, can be that generated in-situ graphene nanometer sheet and molybdenum disulfide nano material height are evenly compound, heat treatment obtains the composite nano materials of graphene nanometer sheet and molybdenum bisuphide later.
(4) Cys contains a plurality of functional group (as: NH
2,-COOH and-SH), these functional groups can provide coordination atom and ion to form coordinate bond.Therefore, Cys can with solution in molybdate Zhong center molybdenum ion form coordination.While is due to the existence of stannic oxide/graphene nano sheet in solution, just formed the coordination mode of stannic oxide/graphene nano sheet-molybdate-Cys, in the reproducibility hydrothermal reaction process, can be that generated in-situ graphene nanometer sheet and molybdenum disulfide nano material height are evenly compound, heat treatment obtains the composite nano materials of graphene nanometer sheet and molybdenum bisuphide later.
(5) existence of graphene nanometer sheet in the intermediate product in preparation process, can suppress the excessive crystal growth of molybdenum bisuphide in heat treatment process and reunite, obtain relative crystallinity and hang down the molybdenum disulfide nano material less with the number of plies and the composite nano materials of graphene nanometer sheet, such composite nano materials has better performance as electrode material and catalyst carrier.
(6) synthesizing graphite alkene of the present invention and MoS
2the method of composite nano materials be also advantageous in that: by adjusting the ratio of synthetic solvent Raw, can obtain Graphene and the MoS of different proportion
2composite nano materials, Graphene and MoS
2the difference of nano material ratio can be adjusted MoS
2the degree of crystallinity of nano material and the number of plies, make the application of its applicable different field.
The accompanying drawing explanation
Fig. 1 Graphene and MoS
2the SEM pattern of composite nano materials.
(a) the synthetic MoS of embodiment 1
2the SEM pattern of nano material;
(b) synthetic Graphene and the MoS of embodiment 1
2the SEM pattern of composite nano materials, Graphene and MoS
2the ratio of amount is 1: 1;
(c) synthetic Graphene and the MoS of embodiment 2
2the SEM pattern of composite nano materials, Graphene and MoS
2the ratio of amount is 2: 1;
(d) synthetic Graphene and the MoS of embodiment 3
2the SEM pattern of composite nano materials, Graphene and MoS
2the ratio of amount is 4: 1.
Fig. 2 Graphene and MoS
2the XRD figure of composite nano materials.
(a) the synthetic MoS of embodiment 1
2the XRD figure of nano material;
(b) synthetic Graphene and the MoS of embodiment 1
2the XRD figure of composite nano materials, Graphene and MoS
2the ratio of amount is 1: 1;
(c) synthetic Graphene and the MoS of embodiment 2
2the XRD figure of composite nano materials, graphene nanometer sheet and MoS
2the ratio of amount is 2: 1;
(d) synthetic graphene nanometer sheet and the MoS of embodiment 3
2the XRD figure of composite nano materials, graphene nanometer sheet and MoS
2the ratio of amount is 4: 1.
The graphene nanometer sheet that Fig. 3 embodiment 2 is synthetic and MoS
2the TEM pattern of composite nano materials, graphene nanometer sheet and MoS
2the ratio of amount is 2: 1.
Embodiment
Embodiment 1: Graphene and MoS
2the preparation method of composite nano materials:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 1.25mmol (0.015g) graphite powder is distributed in the 20mL concentrated sulfuric acid, adds 0.03g KMnO under stirring
4, institute adds KMnO
4quality be 3 times of graphite, stir 30 minutes, temperature rises to 30 ℃ of left and right, adds the 45ml deionized water, stirs 20 minutes, adds the H of 10ml mass concentration 30%
2o
2, stir 5 minutes, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) 1.25mmol (0.303g) molybdic acid is received and is dissolved in the 63ml deionized water, form the solution of 0.02M, add the Cys of 6.25mmol to stir, Cys is 5.0: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 1.25mmol for step (0.015g) adds in this solution, the amount of substance of graphite raw material used is 1: 1 with Molybdenum in Solution acid sodium amount ratio, ultrasonic processing 1.0h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, in 240 ℃ of lower hydro-thermal reactions 24 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials, SEM, EDS and XRD analysis show that composite material is Graphene and MoS
2composite nano materials, Graphene and MoS in composite nano materials
2the ratio of amount be 1: 1.SEM and XRD figure are shown in respectively Fig. 1 and Fig. 2.
As a comparison, 1.25mmol (0.303g) molybdic acid is received and is dissolved in the 63ml deionized water, form the solution of 0.02M, add the Cys of 6.25mmol to stir, Cys is 5.0: 1 with the ratio of the amount of sodium molybdate, this solution is transferred in hydrothermal reaction kettle, in 240 ℃ of lower hydro-thermal reactions 24 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, obtain MoS
2nano material, characterized it with SEM and XRD.SEM and XRD figure are shown in respectively Fig. 1 and Fig. 2.
From the XRD of Fig. 2, can find out, along with in composite material due to the existence that Graphene is arranged, MoS
2the XRD diffraction maximum of nano material (002) face obviously reduces, and MoS is described
2the degree of crystallinity of nano material and the number of plies are reducing gradually, and the existence of Graphene has reduced MoS
2the degree of crystallinity of nano material and the number of plies.
Embodiment 2: Graphene and MoS
2the preparation method of composite nano materials:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 2.5mmol (0.03g) graphite powder is distributed in the 25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be 4 times of graphite, stir 40 minutes, temperature rises to 33 ℃ of left and right, adds the 50ml deionized water, stirs 25 minutes, adds the H of 12ml mass concentration 30%
2o
2, stir 5-10 minute, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) 1.25mmol (0.303g) molybdic acid is received and is dissolved in the 63ml deionized water, form the solution of 0.02M, add the Cys of 7.5mmol to stir, wherein Cys is 6: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 2.5mmol for step (0.03g) adds in this solution, the amount of substance of graphite raw material used is 2: 1 with Molybdenum in Solution acid sodium amount ratio, ultrasonic processing 1.5h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, in 220 ℃ of lower hydro-thermal reactions 28 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials, SEM, EDS, XRD and tem analysis show that composite material is Graphene and MoS
2composite nano materials, Graphene and MoS in composite nano materials
2the ratio of amount be 2: 1.SEM and XRD figure are shown in respectively Fig. 1 and Fig. 2, and TEM figure is shown in Fig. 3.
From the XRD of Fig. 2, can find out, along with the increase of the Graphene in composite material, MoS
2the XRD diffraction maximum of nano material (002) face reduces gradually, and MoS is described
2the degree of crystallinity of nano material and the number of plies are reducing gradually, and the existence of Graphene has reduced MoS
2the degree of crystallinity of nano material and the number of plies.
Embodiment 3: Graphene and MoS
2the preparation method of composite nano materials:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 5.0mmol (0.06g) graphite powder is distributed in the 25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be 4 times of graphite, stir 50 minutes, temperature rises to 35 ℃ of left and right, adds the 50ml deionized water, stirs 30 minutes, adds the H of 20ml mass concentration 30%
2o
2, stir 15 minutes, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) 1.25mmol (0.303g) molybdic acid is received and is dissolved in the 63ml deionized water, form the solution of 0.02M, add the Cys of 15mmol to stir, Cys is 12: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 5.0mmol for step (0.06g) adds in this solution, the amount of substance of graphite raw material used is 4: 1 with Molybdenum in Solution acid sodium amount ratio, ultrasonic processing 2.0h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, in 200 ℃ of lower hydro-thermal reactions 30 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials, SEM, EDS and XRD analysis show that composite material is Graphene and MoS
2composite nano materials, Graphene and MoS in composite nano materials
2the ratio of amount be 4: 1.SEM and XRD figure are shown in respectively Fig. 1 and Fig. 2.
From the XRD of Fig. 2, can find out, along with the increase of the Graphene in composite material, MoS
2the XRD diffraction maximum of nano material (002) face reduces gradually, and MoS is described
2the degree of crystallinity of nano material and the number of plies are reducing gradually, and the existence of Graphene has reduced MoS
2the degree of crystallinity of nano material and the number of plies.
Embodiment 4: Graphene and MoS
2the preparation method of composite nano materials
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 6.0mmol (0.072g) graphite powder is distributed in the 25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be 3.5 times of graphite, stir 50 minutes, temperature rises to 35 ℃ of left and right, adds the 50ml deionized water, stirs 30 minutes, adds the H of 20ml mass concentration 30%
2o
2, stir 10 minutes, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) the 2.0mmol ammonium molybdate is dissolved in the 60ml deionized water, form the solution of 0.03M, add the Cys of 16mmol to stir, Cys is 8: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 6.0mmol for step (0.072g) adds in this solution, the amount of substance X of graphite raw material used is 2.5: 1 with Molybdenum in Solution acid sodium amount ratio, ultrasonic processing 2.0h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, in 240 ℃ of lower hydro-thermal reactions 36 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials, SEM, EDS and XRD analysis show that composite material is Graphene and MoS
2composite nano materials, Graphene and MoS in composite nano materials
2the ratio of amount be 3: 1.
Embodiment 5: Graphene and MoS
2the preparation method of composite nano materials:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 4.5mmol (0.054g) graphite powder is distributed in the 25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be 3 times of graphite, stir 40 minutes, temperature rises to 30 ℃ of left and right, adds the 50ml deionized water, stirs 24 minutes, adds the H of 20ml mass concentration 30%
2o
2, stir 10 minutes, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) the 1.5mmol ammonium molybdate is dissolved in the 60ml deionized water, form the solution of 0.03M, add the Cys of 15mmol to stir, Cys is 10: 1 with the ratio of the amount of ammonium molybdate, after fully stirring, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 4.5mmol for step (0.054g) adds in this solution, the amount of substance of graphite raw material used is 3: 1 with Molybdenum in Solution acid sodium amount ratio, ultrasonic processing 1.5h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, in 220 ℃ of lower hydro-thermal reactions 26 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, finally at 90%N
2-10%H
2in atmosphere, 900 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials, SEM, EDS and XRD analysis show that composite material is Graphene and MoS
2composite nano materials, Graphene and MoS in composite nano materials
2the ratio of amount be 3: 1.
Embodiment 6: Graphene and MoS
2the preparation method of composite nano materials:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 4.2mmol (0.051g) graphite powder is distributed in the 25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be 4 times of graphite, stir 52 minutes, temperature rises to 32 ℃ of left and right, adds the 40ml deionized water, stirs 15 minutes, adds the H of 15ml mass concentration 30%
2o
2, stir 8 minutes, through centrifugation, with after mass concentration 5%HCl solution, deionized water and acetone cyclic washing, obtaining the graphite oxide nanometer sheet;
2) the 4.2mmol ammonium molybdate is dissolved in the 60ml deionized water, form the solution of 0.07M, add the Cys of 25.2mmol to stir, Cys is 6: 1 with the ratio of the amount of ammonium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 4.2mmol for step (0.051g) adds in this solution, the amount of substance X of graphite raw material used is 1: 1 with Molybdenum in Solution acid sodium amount ratio, ultrasonic processing 1.5h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, in 230 ℃ of lower hydro-thermal reactions 25 hours, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, finally at 90%N
2-10%H
2in atmosphere, 1000 ℃ of heat treatment 2h, obtain Graphene and MoS
2composite nano materials, SEM, EDS and XRD analysis show that composite material is Graphene and MoS
2composite nano materials, Graphene and MoS in composite nano materials
2the ratio of amount be 1: 1.
Claims (2)
1. a Graphene and MoS
2composite nano materials, it is characterized in that composite material is by Graphene and MoS
2the compound formation of nano material, Graphene and MoS
2between nano material, the ratio of amount is 1: 1-4: 1;
Described Graphene and MoS
2the preparation method of composite nano materials carry out as follows: the 1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, the 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, under stirring, adds KMnO
4, institute adds KMnO
4quality be graphite powder 3-4 doubly, stir 30-60 minute, temperature rises to 30-35 ℃, adds the 40-50ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30%
2o
2, stir 5-20 minute, through centrifugation, after HCl solution, deionized water and acetone cyclic washing by mass concentration 5%, obtain the graphite oxide nanometer sheet;
2) molybdate is dissolved in deionized water to the solution that forms 0.02～0.07M, adding Cys is sulphur source and reducing agent, Cys is 5: 1～12: 1 with the ratio of the amount of molybdate, again will be by the 1st) the preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) step graphite raw material amount used is 1: 1～4: 1 with the ratio of the amount of molybdate, ultrasonic processing 1-2h, the graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, this mixture is proceeded in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and seal, at 200-240 ℃ of reaction 20-36h, the product obtained is through centrifugation, and with deionized water and absolute ethanol washing, dry, finally at 90%N
2-10%H
2in atmosphere, 800-1000 ℃ of heat treatment 2h, obtain graphene nanometer sheet and MoS
2composite nano materials.
2. a kind of Graphene according to claim 1 and MoS
2composite nano materials, it is characterized in that described molybdate is sodium molybdate or ammonium molybdate.
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Family Cites Families (4)
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| TWI640478B (en) * | 2018-01-15 | 2018-11-11 | National Taiwan Normal University | Synthesis method of carboxyl-modified molybdenum disulfide |
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