CN102694171A - Hydrothermal preparation method for composite material of single-layer WS2 and graphene - Google Patents

Hydrothermal preparation method for composite material of single-layer WS2 and graphene Download PDF

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CN102694171A
CN102694171A CN2012101878546A CN201210187854A CN102694171A CN 102694171 A CN102694171 A CN 102694171A CN 2012101878546 A CN2012101878546 A CN 2012101878546A CN 201210187854 A CN201210187854 A CN 201210187854A CN 102694171 A CN102694171 A CN 102694171A
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graphene
individual layer
sodium tungstate
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CN102694171B (en
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陈卫祥
黄国创
王臻
马琳
李�赫
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Zhejiang University ZJU
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Abstract

The invention discloses a hydrothermal preparation method for a composite material of single-layer WS2 and graphene. A composite nanometer material consists of the single-layer WS2 and the graphene, which are compounded, wherein the mass ratio of the single-layer WS2 to the graphene is 1:1 to 1:4. The method comprises the following steps of: ultrasonically dispersing a graphene oxide into de-ionized water, sequentially adding a cationic surfactant, L-cysteine and sodium tungstate with stirring, transferring a mixed disperse system into a hydrothermal reaction kettle, performing hydrothermal reaction for 24 hours at 180 to 200 DEG C, naturally cooling a reaction product, centrifugally collecting solid products, washing the solid products by using the de-ionized water, drying the washed solid products, and performing heat treatment in a nitrogen/hydrogen mixed atmosphere to obtain the composite nanometer material of the single-layer WS2 and the graphene. A process is simple, and the consumption of an organic solvent is avoided.

Description

A kind of individual layer WS 2Hydrothermal preparing process with graphene composite material
Technical field
The present invention relates to individual layer WS 2With the hydrothermal preparing process of graphene composite material, belong to the inorganic composite nano technical field of material.
Background technology
Recently, the research of individual layer two-dimensional nano material has caused people's very big interest.As everyone knows, Graphene is present 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 prospects.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 WS of single layer structure 2And MoS 2
WS 2Typical layered structure with similar graphite.WS 2Layer structure is the layer structure of sandwich, and (S-W-S) is very strong covalent bonds in its layer, and interlayer then is more weak Van der Waals force, peels off easily between layer and the layer.WS with layer structure 2As material of main part, through inserting reaction, object atom or molecule can be inserted in and form intercalation compound between body layer.Because WS 2Between the layer of lamellar compound and the layer is to combine through more weak Van der Waals force, so can allow through intercalation at interlayer introducing external atom or molecule.Therefore, WS 2Lamellar compound is a kind of up-and-coming electrochemical lithium storage electrode material.But as the electrode material of electrochemical reaction, WS 2Electric conductivity relatively poor.
The inorganic compound of layer structure, but its number of plies (below 5 layers) more after a little while, its Electronic Performance and its number of plies have substantial connection.Research recently discloses and compares the WS of single layer structure with body phase material 2Have uncommon physical chemistry and photoelectric properties, as: the WS of single layer structure 2Raman spectrum obvious variation is arranged; The WS of single layer structure 2Also shown good performance as lithium ion battery negative material.But because WS 2Be semi-conducting material in essence, its electronic conductivity is not high enough, strengthens its electric conductivity as the electrode material application need.
Because individual layer WS 2Have similar two-dimensional nano sheet pattern with Graphene, both have good similitude on microscopic appearance and crystal structure.Individual layer WS 2With graphene nanometer sheet can be as electrode material and catalyst applications.If with individual layer WS 2Composite material with the compound preparation of graphene nanometer sheet; The high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite material; Strengthen the electron transport in electrochemical electrode reaction and the catalytic reaction process, can further improve the chemical property and the catalytic performance of composite material.Individual layer WS in addition 2Compound with graphene nanometer sheet, the big Π key of graphene nanometer sheet can with WS 2The interaction of surface electronic structure further strengthens the ability of electron transport and charge migration.Therefore, this individual layer WS 2Has the performance of using widely and strengthening as electrode material and catalyst carrier etc. with the composite nano materials of graphene nanometer sheet.
But, up to the present, individual layer WS 2Preparation mainly be based on the insertion of lithium ion and the method for peeling 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, need the long time.Consider from large-scale application, research and develop a kind of individual layer WS for preparing simply and easily 2With the method for graphene composite material still be a challenging job.
The present invention adopts cationic surfactant, and graphene oxide and sodium tungstate are raw material, prepares individual layer WS with hydro-thermal reaction easily 2Composite material with Graphene.But so far, this method yet there are no public reported.
Summary of the invention
The object of the present invention is to provide OnePlant individual layer WS 2Hydrothermal preparing process with graphene composite material.
Individual layer WS 2With the hydrothermal preparing process of graphene composite material, this composite material is by individual layer WS 2With the compound formation of Graphene, individual layer WS 2And the ratio of the amount between the Graphene is 1:1-1:4, and its preparation process is following:
(1) is dispersed in the deionized water graphene oxide is ultrasonic, adds cationic surfactant then, and fully stir;
(2) L-cysteine and sodium tungstate are joined in the mixed system that step (1) obtains successively; And constantly stirring is dissolved L-cysteine and sodium tungstate fully; Add hydroxylamine hydrochloride again and mix; Sodium tungstate is 1:5 with the ratio of the amount of L-cysteine consumption, and the ratio of the amount between sodium tungstate and the hydroxylamine hydrochloride is 1:3-1:5, and the ratio of sodium tungstate and the amount of graphene oxide is at 1:1-1:4;
(3) resulting mixed dispersion is moved on in the hydrothermal reaction kettle, and add 80% of deionized water adjustment volume to hydrothermal reaction kettle nominal volume, cationic surfactant concentration is 0.02-0.05 M; The content of graphene oxide is put into this agitated reactor in the constant temperature oven for 31.25-62.5 mmol/L; Behind 180-200 ℃ of following hydro-thermal reaction 24 h, let it naturally cool to room temperature, collect solid product with centrifugation; And fully wash with deionized water, 100 ℃ of following vacuumizes;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Above-mentioned graphene oxide can adopt improved Hummers method preparation.
Among the present invention, described cationic surfactant is a softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide.
Hydrothermal method of assisting with cationic surfactant of the present invention prepares individual layer WS 2Have the following advantages with the method for Graphene composite nano materials: graphene oxide surface and edge have a lot of oxygen-containing functional groups (like hydroxyl; Carbonyl; Carboxyl); These oxygen-containing functional groups more easily are dispersed in water or the organic liquid graphene oxide, but these oxygen-containing functional groups make the graphene oxide surface have negative electrical charge, make graphene oxide with have the WS of negative electrical charge 4 2-Ion is incompatible, and the present invention is adsorbed onto the graphene oxide surface with cationic surfactant earlier through electrostatic interaction, and make it have the part positive charge, and then mix with the sulfo-ammonium tungstate, since electrostatic interaction, WS 4 2-Ion just interacts with the graphene oxide that has adsorbed cationic surfactant easily and combines, and just prepares individual layer WS through hydro-thermal reaction and heat treatment subsequently again 2With graphene composite material.The inventive method has technology characteristics simply and easily, need not consume organic solvent.
Description of drawings
Fig. 1 is the individual layer WS of embodiment 1 preparation 2The XRD diffraction pattern of/graphene composite material, * is individual layer WS among the figure 2With individual layer WS 2Between interlamellar spacing;
Fig. 2Be the individual layer WS of embodiment 1 preparation 2/ graphene composite material SEM pattern;
Fig. 3Be the individual layer WS of embodiment 1 preparation 2/ graphene composite material HRTEM figure.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Graphene oxide in the following instance adopts improved Hummers method preparation: 0 oUnder the 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 KMnO under constantly stirring 4, institute adds KMnO 4Quality be 4 times of graphite powder, stirred 50 minutes, when temperature rises to 35 ℃, slowly add 50 ml deionized waters, stirred again 30 minutes, add the H of 15 ml mass concentrations 30% 2O 2, stirred 30 minutes, through centrifugation, successively with obtaining graphene oxide behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing.
Embodiment 1.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 1.6 mmol softex kw cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 6.2 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 190 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, its XRD sees Fig. 1, SEM sees Fig. 2, HRTEM sees Fig. 3.Obtaining product after the characterization result demonstration heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:2 with the Graphene amount.
Embodiment 2.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 2.4 mmol softex kw cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 4.96 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 180 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:2 with the Graphene amount.
Embodiment 3.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 4.0 mmol softex kw cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 3.72 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 200 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, prepares individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:2 with the Graphene amount.
Embodiment 4.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 4.0 mmol softex kw cationic surfactants again, and fully stir;
2) then add 1.50g (12.38 mmol) L-cysteine and 0.818g (2.48 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 7.44 mmol mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 190 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:1 with the Graphene amount.
Embodiment 5.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 4.0 mmol DTAB cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 3.72 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 190 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:2 with the Graphene amount.
Embodiment 6.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 4.0 mmol, eight alkyl trimethyl ammonium bromide cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 3.72 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 190 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:2 with the Graphene amount.
Embodiment 7.
1) is dispersed in the 60 mL deionized waters 3.75 mmol graphene oxides are ultrasonic, adds 3.2 mmol softex kw cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 3.72 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 180 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:3 with the Graphene amount.
Embodiment 8.
1) is dispersed in the 60 mL deionized waters 5.0 mmol graphene oxides are ultrasonic, adds 1.6 mmol softex kw cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 3.72 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 200 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:4 with the Graphene amount.
Embodiment 9.
1) is dispersed in the 60 mL deionized waters 2.5 mmol graphene oxides are ultrasonic, adds 2.4 mmol tetra-n-butyl ammonium bromide cationic surfactants again, and fully stir;
2) then add 0.75g (6.19 mmol) L-cysteine and 0.41g (1.24 mmol) sodium tungstate (Na successively 2WO 42H 2O), and constantly stir L-cysteine and sodium tungstate are dissolved fully, add 3.72 mmol hydroxylamine hydrochloride (NH again 2OHHCl) and mix;
3) resulting mixed system is transferred in the hydrothermal reaction kettle of 100 mL; And add deionized water adjustment volume to 80 mL to the hydrothermal reaction kettle nominal volume, this agitated reactor is put in the constant temperature oven, behind 200 ℃ of following hydro-thermal reaction 24 h; Let it naturally cool to room temperature; Collect solid product with centrifugation, and fully wash, 100 ℃ of following vacuumizes with deionized water;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2 h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
Use XRD, SEM and HRTEM to heat treatment after resultant end product characterize, characterization result shows that obtaining product after the heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2Ratio=1:2 with the Graphene amount.

Claims (2)

1. OnePlant individual layer WS 2With the hydrothermal preparing process of graphene composite material, this composite material is by individual layer WS 2With the compound formation of Graphene, individual layer WS 2And the ratio of the amount between the Graphene is 1:1-1:4, and its preparation process is following:
(1) is dispersed in the deionized water graphene oxide is ultrasonic, adds cationic surfactant then, and fully stir;
(2) L-cysteine and sodium tungstate are joined in the mixed system that step (1) obtains successively; And constantly stirring is dissolved L-cysteine and sodium tungstate fully; Add hydroxylamine hydrochloride again and mix; Sodium tungstate is 1:5 with the ratio of the amount of L-cysteine consumption, and the ratio of the amount between sodium tungstate and the hydroxylamine hydrochloride is 1:3-1:5, and the ratio of sodium tungstate and the amount of graphene oxide is at 1:1-1:4;
(3) resulting mixed dispersion is moved on in the hydrothermal reaction kettle, and add 80% of deionized water adjustment volume to hydrothermal reaction kettle nominal volume, cationic surfactant concentration is 0.02-0.05 M; The content of graphene oxide is put into this agitated reactor in the constant temperature oven for 31.25-62.5 mmol/L; Behind 180-200 ℃ of following hydro-thermal reaction 24 h, let it naturally cool to room temperature, collect solid product with centrifugation; And fully wash with deionized water, 100 ℃ of following vacuumizes;
(4) with above-mentioned resulting solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ of following heat treatment 2h, the volume ratio of hydrogen is 10% in the mist, obtains individual layer WS 2Composite nano materials with Graphene.
2. by the described individual layer WS of claim 1 2With the hydrothermal preparing process of graphene composite material, it is characterized in that described cationic surfactant is a softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide.
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