CN102694171B - 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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CN102694171B
CN102694171B CN201210187854.6A CN201210187854A CN102694171B CN 102694171 B CN102694171 B CN 102694171B CN 201210187854 A CN201210187854 A CN 201210187854A CN 102694171 B CN102694171 B CN 102694171B
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graphene
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CN102694171A (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 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 current maximum individual layer two-dimensional nano materials of research, and Graphene has the performances such as physics, chemistry and the 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 WS of single layer structure 2and MoS 2.
WS 2there is the typical layered structure of similar graphite.WS 2layer structure is the layer structure of sandwich, and in its layer, (S-W-S) is very strong covalent bonds, and interlayer is weak Van der Waals force, easily peels off between layers.There is the WS of layer structure 2as material of main part, react by insertion, object atom or molecule can be inserted in and between body layer, form intercalation compound.Due to WS 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, 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 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 compared with body phase material, the WS of single layer structure 2there are uncommon physical chemistry and photoelectric properties, as: the WS of single layer structure 2raman spectrum have obvious variation; The WS of single layer structure 2also shown good performance as lithium ion battery negative material.But due to WS 2be semi-conducting material in essence, its electronic conductivity is not high enough, and as electrode material, application need to strengthen its electric conductivity.
Due to 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 2can serve as electrode material and catalyst application with graphene nanometer sheet.If by 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 electronics transmission in electrochemical electrode reaction and catalytic reaction process, can further improve chemical property and the catalytic performance of composite material.Individual layer WS in addition 2compound with graphene nanometer sheet, the large Π key of graphene nanometer sheet can with WS 2the interaction of Electronic Structure, further strengthens the ability of electronics transmission and charge migration.Therefore, this individual layer WS 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 WS 2preparation be mainly the insertion based on lithium ion and the method peeled off, there is following shortcoming in this method: to the environment high such as air, moisture sensitivity, need to consume a large amount of organic solvents, time that need to be longer.Consider from large-scale application, research and development one is prepared individual layer WS simply and easily 2with the method for graphene composite material be still a challenging job.
The present invention adopts cationic surfactant, and graphene oxide and sodium tungstate are raw material, prepares individual layer WS by hydro-thermal reaction easily 2composite material 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 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 Graphene is 1:1-1:4, and its preparation process is as follows:
(1) be dispersed in deionized water ultrasonic graphene oxide, then add cationic surfactant, and fully stir;
(2) Cys and sodium tungstate are joined successively in the mixed system that step (1) obtains, and constantly stir Cys and sodium tungstate are dissolved completely, add again hydroxylamine hydrochloride and be uniformly mixed, sodium tungstate is 1:5 with the ratio of the amount of Cys consumption, the ratio of the amount between sodium tungstate and hydroxylamine hydrochloride is 1:3-1:5, sodium tungstate with the ratio of the amount of graphene oxide at 1:1-1:4;
(3) obtained mixed dispersion is moved on 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 that 31.25-62.5 mmol/L puts into this reactor in constant temperature oven, at 180-200 ℃, after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained 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 WS 2composite nano materials with Graphene.
Above-mentioned graphene oxide can adopt improved Hummers method preparation.
In the present invention, described cationic surfactant is softex kw, DTAB, eight alkyl trimethyl ammonium bromides or tetra-n-butyl ammonium bromide.
Hydrothermal method with cationic surfactant assistance of the present invention is prepared individual layer WS 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 and the WS with negative electrical charge 4 2-ion is incompatible, and the present invention is first adsorbed onto cationic surfactant graphene oxide surface by electrostatic interaction, makes it with part positive charge, and then mixes with sulfo-ammonium tungstate, due to electrostatic interaction, and WS 4 2-ion just easily interacts and combines with the graphene oxide that has adsorbed cationic surfactant, more just prepares individual layer WS by hydro-thermal reaction and heat treatment subsequently 2with graphene composite material.The inventive method has technique feature simply and easily, does not need to consume organic solvent.
Accompanying drawing explanation
Fig. 1 is individual layer WS prepared by embodiment 1 2the XRD diffraction pattern of/graphene composite material, in figure, * is individual layer WS 2with individual layer WS 2between interlamellar spacing;
fig. 2individual layer WS prepared by embodiment 1 2/ graphene composite material SEM pattern;
fig. 3individual layer WS prepared by embodiment 1 2/ graphene composite material HRTEM figure.
Embodiment
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0 ounder C ice bath, by 5.0-10.0 mmol, (0.06-0.12 g) graphite powder dispersed with stirring, in the 30 mL concentrated sulfuric acids, slowly adds KMnO under constantly stirring 4, institute adds KMnO 4quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise 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 ultrasonic 2.5 mmol graphene oxides, then add 1.6 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 6.2 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 190 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, its XRD is shown in Fig. 1, SEM is shown in Fig. 2, HRTEM is shown in Fig. 3.After characterization result demonstration heat treatment, obtaining product is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:2 with Graphene amount.
Embodiment 2.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add 2.4 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 4.96 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 180 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:2 with Graphene amount.
Embodiment 3.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add 4.0 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 3.72 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 200 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, prepares individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:2 with Graphene amount.
Embodiment 4.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add 4.0 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 1.50g (12.38 mmol) Cys and 0.818g (2.48 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 7.44 mmol mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 190 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:1 with Graphene amount.
Embodiment 5.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add 4.0 mmol DTAB cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 3.72 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 190 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:2 with Graphene amount.
Embodiment 6.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, 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 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 3.72 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 190 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:2 with Graphene amount.
Embodiment 7.
1) be dispersed in 60 mL deionized waters ultrasonic 3.75 mmol graphene oxides, then add 3.2 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 3.72 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 180 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:3 with Graphene amount.
Embodiment 8.
1) be dispersed in 60 mL deionized waters ultrasonic 5.0 mmol graphene oxides, then add 1.6 mmol softex kw cationic surfactants, and fully stir;
2) then add successively 0.75g (6.19 mmol) Cys and 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 3.72 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 200 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:4 with Graphene amount.
Embodiment 9.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, 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 0.41g (1.24 mmol) sodium tungstate (Na 2wO 42H 2o), and constantly stir Cys and sodium tungstate are dissolved completely, then add 3.72 mmol hydroxylamine hydrochloride (NH 2and be uniformly mixed OHHCl);
3) obtained mixed system is transferred in the hydrothermal reaction kettle of 100 mL, and add deionized water to adjust volume to 80 mL to hydrothermal reaction kettle nominal volume, this reactor is put in constant temperature oven, at 200 ℃ after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 ℃ heat treatment 2 h, in mist, the volume ratio of hydrogen is 10%, obtains individual layer WS 2composite nano materials with Graphene.
With XRD, SEM and HRTEM to heat treatment after the end product that obtains characterize, characterization result shows that obtaining product after heat treatment is individual layer WS 2/ graphene composite material, wherein WS 2ratio=1:2 with Graphene amount.

Claims (1)

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 of substance between Graphene is 1:1-1:4, and its preparation process is as follows:
(1) be dispersed in deionized water ultrasonic graphene oxide, 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 tungstate are joined successively in the mixed system that step (1) obtains, and constantly stir Cys and sodium tungstate are dissolved completely, add again hydroxylamine hydrochloride and be uniformly mixed, sodium tungstate is 1:5 with the ratio of the amount of substance of Cys consumption, the ratio of the amount of substance between sodium tungstate and hydroxylamine hydrochloride is 1:3-1:5, sodium tungstate with the ratio of the amount of substance of graphene oxide at 1:1-1:4;
(3) obtained mixed dispersion is moved on 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 that 31.25-62.5 mmol/L puts into this reactor in constant temperature oven, at 180-200 ℃, after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash vacuumize at 100 ℃ with deionized water;
(4) by above-mentioned obtained 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 WS 2composite nano materials with Graphene.
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