CN106564954B - A kind of method that low-temperature reduction prepares class graphene molybdenum disulfide - Google Patents
A kind of method that low-temperature reduction prepares class graphene molybdenum disulfide Download PDFInfo
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Abstract
The present invention provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, this method comprises the following steps：Step 1, molybdenum disulfide powder is added in intercalation solution and carries out intercalation, the mixed solution that the intercalation solution is potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide form；Step 2, intercalation molybdenum disulfide powder made from step 1 is added in reducing agent and carries out reduction reaction, and the reducing agent is dimethylformamide or dimethylacetylamide.The method that the present invention prepares class graphene molybdenum disulfide by way of graft process and low-temperature reduction method combine, using the mixed solution of the concentrated sulfuric acid, potassium chlorate, sodium nitrate and hydrogen peroxide composition as intercalation solution, using dimethylformamide or dimethylacetylamide as reducing agent, above-mentioned intercalation solution and reducing agent coordinated, along with the cooperation of specific reaction condition, class graphene molybdenum disulfide is finally made.
Description
Technical field
The invention belongs to New Two Dimensional Material Field, is related to class graphene molybdenum disulfide, and in particular to a kind of low-temperature reduction
The method for preparing class graphene molybdenum disulfide.
Background technology
The class graphene molybdenum disulfide (Graphene-like molybdenum disulfide) being made of few layer of molybdenum disulfide is that one kind has
New Two Dimensional (2D) lamellar compound of similar graphene-structured and performance.In recent years with its unique physics, chemical property and
As emerging research hotspot.Class graphene molybdenum disulfide has " Sanming City by what the multilayer molybdenum disulfide of hexagonal crystal system formed
Control sandwich " the two dimensional crystal material of layer structure, individual layer molybdenum disulfide is made of three layers of atomic layer, and middle one layer is molybdenum atom
Layer, upper and lower two layers is sulphur atom layer, and molybdenum atom layer forms class " sandwich " structure folded by two layers of sulphur atom layer, and molybdenum is former
Son forms two-dimensional atomic crystal with sulphur atom with Covalent bonding together；Multilayer molybdenum disulfide is made of some individual layer molybdenum disulfide, and one
As be no more than five layers, for interlayer there are weak Van der Waals force, interlamellar spacing is about 0.65nm.
As a kind of important two-dimensional layer nano material, few layer molybdenum disulfide is being lubricated with its unique layer structure
The various fields such as agent, catalysis, energy stores, photoelectric material, semiconductor devices, composite material are widely used.Compared to graphene
Zero band gap, class graphene molybdenum disulfide possesses brighter prospect in field of photoelectric devices there are regulatable band gap；
Compared to the three-dimensional bulk structure of silicon materials, class graphene molybdenum disulfide has the two-dimensional layered structure of nanoscale, can by with
To manufacture semiconductor or specification smaller, the electronic chip of efficiency higher, will be obtained in fields such as follow-on nano-electric devices
Extensive use.
Experiment proves the ability that molybdenum disulfide has electrocatalytic hydrogen evolution reaction, has many liberations of hydrogen anti-at the edge of molybdenum disulfide
Active site position (the Science.2007,317 (5834) answered:100-102).According to this experimental evidence, with reference to molybdenum disulfide sheet
The characteristic of semiconductor and optical absorption characteristics of body, it is anti-can to speculate that molybdenum disulfide can be used as photochemical catalyst to be used for photocatalysis production oxygen
Should.But since molybdenum disulfide belongs to narrow-band semiconductor in itself, it is not very strong that this, which has just been doomed its oxidability, is individually used for light
During catalyst therefore its catalytic activity may be restricted and influence.Research shows that molybdenum disulfide is deposited on the synthesis of CdS surfaces
Efficient visible ray production hydrogen photochemical catalyst, its highest photocatalysis production oxygen activity are 36 times of (Journal of the of CdS
American Chemical Society.2008,130(23):7176-7177).This demonstrate that molybdenum disulfide is good light
The co-catalyst of catalysis production hydrogen reaction, and for molybdenum disulfide Liao Yitiaoxin roads are hewed out for Photocatalyzed Hydrogen Production.Meanwhile curing
The controllable band gap of molybdenum makes it possess potentiality in electrode material and energy storage field, also therefore be subject to researcher extensive concern and
As research hotspot in recent years.
At present, the preparation method that can be used for class graphene molybdenum disulfide mainly has：Micromechanical forces stripping method, lithium from
The stripping method and high temperature thermal decomposition, vapour deposition, hydro-thermal method of " from top to bottom " such as sub- graft process, liquid phase ultrasonic methods etc. are " under
On and " synthetic method.Mechanical stripping method belongs to a kind of relatively ripe two-dimensional layer material preparation method, by special
Adhesive tape overcomes the effect of the intermolecular Van der Waals force of molybdenum disulfide to realize stripping, finally obtains thinned at least layer even individual layer
Method；Although mechanical stripping method is simple and practicable, the stripping of the monoatomic layer thickness of class graphene molybdenum disulfide high-crystallinity is realized
From, but poor repeatability causes it to be difficult to meet the needs of preparing on a large scale.Lithium ion graft process is then to grow up
A kind of method, increase molybdenum disulfide interlamellar spacing by adding the intercalator of such as n-BuLi, after vigorous reaction to reduce
Van der Waals interaction, is then ultrasonically treated, to obtain few layer to the class graphene molybdenum disulfide of individual layer；It is advantageous that gained class
Graphene molybdenum disulfide quality is taught and extent of exfoliation is higher；Have been developed that at present it is a variety of under the conditions of lithium ion intercalation side
Method, such as solvent Li graft process, solvent-free Li intercalations stripping method, electrochemistry Li insertions and hydro-thermal auxiliary Li graft process etc..It is super
Sound method is typically that original molybdenum disulfide powder is added in the specific organic solvent of certain class even water, is then shaken by ultrasonic wave
The stripping between layer of molybdenum-disulfide is realized in the effect swung；Ultrasonic method is easy to operate, it is easy to accomplish the requirement largely prepared, but peel off
Overlong time and the restriction that charge stripping efficiency is not high when becoming its use.
Hydro-thermal method and hot solvent method are in certain closed reaction vessel, using water or specific solvent as medium, are made in heating
With a kind of lower method completed synthesis and prepared.The advantage of this kind of method is that reaction temperature is not high and process is easily controllable；It is logical
Hydro-thermal method or hot solvent method are crossed, people can usually prepare the two-dimensional material of special appearance.Chemical vapor deposition (CVD) method
Its principle is the thermal decomposition for the solid precursor for realizing Mo and S at high temperature, the Mo discharged and S atom is deposited on selected
In substrate, so as to grow into the method for two-dimensional film.CVD method through examine be proved to be conducive to prepare high surface area, thickness it is controllable
And possess the class graphene curing of excellent Electronic Performance, it is the preparation method of a kind of common " from bottom to top ".
The number of applying for a patent is that 201410027158.8 Chinese patent discloses the preparation of a species graphene molybdenum disulfide
Method, it is concretely comprised the following steps：1) sulphur powder is heated to be sulfur vapor；2) sulfur vapor is blown into using carrier gas and is equipped with substrate and three oxidations
The reaction chamber of molybdenum powder；3) reaction chamber temperature is heated to 100-600 DEG C of insulation 10-30min, then heats reaction chamber temperature
To 650-900 DEG C of heating 5-60min, individual layer molybdenum disulfide can be finally formed on substrate.
The Chinese patent that the number of applying for a patent is 201410512418.0 discloses a kind of ultrasound assisted chemical intercalation and prepares two
The method of molybdenum sulfide, its specific steps include：1) by molybdenum disulfide powder and n-BuLi under the protection of high-purity argon gas, in room
Warm supervital reaction 0.3-3h；2) unreacted n-BuLi is removed, lithium intercalation molybdenum disulfide powder is obtained, adds advance deoxygenation
Ultra-pure water, reacts 0.5-2h under ultrasound condition, and stripping obtains the crude product of molybdenum disulfide nano sheet；3) a certain amount of second is measured
Alcohol, adds reaction gained molybdenum disulfide nano sheet and 5-20min is centrifuged under 10000-26000rmp rotating speeds, collect centrifugation bottom of the tube
Product；4) a certain amount of ultra-pure water is measured, suspension is made into gained molybdenum disulfide nano sheet, under 2000-8000rmp rotating speeds
10-40min is centrifuged, precipitation is discarded, upper strata product is centrifuged into 10-100min under the conditions of 10000-26000rmp, discards upper strata
Clear liquid, reservation not separation product, product is distributed in a certain amount of ultra-pure water, is repeated above steps by centrifugation, is obtained most
End-product.
Although mean disclosed above adds chemical method that class graphene molybdenum disulfide has been made using chemical synthesis or physics,
But the big multipaths of these preparation methods is more, high to equipment requirement and complicated, and some is more demanding to conditions such as temperature, energy consumption
It is larger.Therefore, the simple method for preparing for exploring the class graphene molybdenum disulfide that a kind of flow is simple and energy consumption is relatively low is very necessary.
The content of the invention
Based on problems of the prior art, the present invention proposes a kind of low-temperature reduction and prepares class graphene molybdenum disulfide
Method, solve that existing preparation method flow is complicated and the technical problem of high energy consumption.
In order to solve the above-mentioned technical problem, the application, which adopts the following technical scheme that, is achieved：
A kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, this method comprise the following steps：
Step 1, molybdenum disulfide powder is added in intercalation solution and carries out intercalation, is filtered, is dried after the completion of reaction
It is dry, obtain intercalation molybdenum disulfide powder；
The mixed solution that the intercalation solution is potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide form；
The molybdenum disulfide powder and potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and mass concentration 30%
Hydrogen peroxide between proportion relation be 1g：(1~4) g：(0.5~2) g：(9~40) mL：(4~20) mL.
Step 2, intercalation molybdenum disulfide powder made from step 1 is added in reducing agent and carries out reduction reaction, reaction
By filtering after completely, class graphene molybdenum disulfide is obtained after dry and grinding；
The reducing agent is dimethylformamide or dimethylacetylamide.
The present invention also has following distinguishing feature：
Preferably, the molybdenum disulfide powder and potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and quality are dense
Proportion relation between the hydrogen peroxide of degree 30% is 1g：2g：1g：23mL：7mL.
Specifically, the proportion relation between the intercalation molybdenum disulfide powder and dimethylformamide is 2g：(750~
1200)mL；Proportion relation between the intercalation molybdenum disulfide powder and dimethylacetylamide is 2g：(615~750) mL.
Preferably, the proportion relation between the intercalation molybdenum disulfide powder and dimethylacetylamide is 2g：700mL.
Dispersant can also be added in step 2.
Preferably, the dispersant is 1-methyl-2-pyrrolidinone or polyvinylpyrrolidone.
Specifically, the proportion relation between the intercalation molybdenum disulfide powder and dispersant is 2g：(62~100) mL.
Specifically, in step 1, the process of the intercalation is：Molybdenum disulfide powder is added in mixed solution,
10~30 DEG C of 1~3h of reaction are heated to, then at 30~70 DEG C and stir 20~50min, stirring reaction 10 at 75~100 DEG C~
30min, then filters, is dry, obtaining intercalation molybdenum disulfide powder.
Specifically, in step 2, the process of the reduction reaction is：By intercalation molybdenum disulfide powder made from step 1
It is added in reducing agent, reacts 10~40min, wash products is filtered with deionized water while hot, then 90~120 in drying box
Dry 18~24h, that is, obtain class graphene molybdenum disulfide at DEG C；
The reduction reaction temperature when dimethylformamide is as reducing agent is 130~160 DEG C, the dimethyl
Reduction reaction temperature when acetamide is as reducing agent is 140~180 DEG C.
Compared with prior art, the present invention beneficial has the technical effect that：
(I) method that the present invention prepares class graphene molybdenum disulfide by way of graft process and low-temperature reduction method combine,
Using the mixed solution of the concentrated sulfuric acid, potassium chlorate, sodium nitrate and hydrogen peroxide composition as intercalation solution, using dimethylformamide or
Dimethylacetylamide is as reducing agent, above-mentioned intercalation solution and reducing agent coordinated, along with matching somebody with somebody for specific reaction condition
Close, finally obtained class graphene molybdenum disulfide.
(II) method of the invention prepares class graphene molybdenum disulfide, obtains with nanoscale, the class stone of superior performance
Black alkene molybdenum disulfide, solves the harsh skills of reaction condition such as existing class graphene molybdenum disulfide preparation flow complexity, temperature
Art problem.It is easy to operate, it is not necessary to which that complicated and cumbersome preparation facilities, relatively low, preparation efficiency is required to preparation conditions such as temperature
Height, yield is big, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is the Raman collection of illustrative plates of the class graphene molybdenum disulfide in embodiment 1.
Fig. 2 is the SEM figures of the class graphene molybdenum disulfide in embodiment 1.
Fig. 3 is the Raman collection of illustrative plates of the molybdenum disulfide in comparative example 1.
Fig. 4 is the SEM figures of the molybdenum disulfide in comparative example 1.
Fig. 5 is the Raman collection of illustrative plates of the molybdenum disulfide in comparative example 3.
Fig. 6 is the SEM figures of the molybdenum disulfide in comparative example 3.
The particular content of the present invention is described in more detail with reference to embodiments.
Embodiment
It should be noted that heretofore described class graphene molybdenum disulfide is the molybdenum disulfide of few Rotating fields, it is described
The structure that few Rotating fields are 1~5 layer.
Above-mentioned technical proposal is deferred to, the specific embodiment of the present invention is given below, it is necessary to which explanation is the present invention not office
It is limited to specific examples below, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.The present invention is described in further details with reference to embodiment.
Embodiment 1：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 20g, sodium nitrate 10g, the concentrated sulfuric acid of mass concentration 98% be 230mL
Hydrogen peroxide with mass concentration 30% is 70mL；
Then heating water bath at 30 DEG C and stirs 30min, carries out intercalation, be then heated to 75 to 15 DEG C of reaction 2h
DEG C stirring reaction 30min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 700mL's
Dimethylacetylamide, is reduction reaction 30min at 160 DEG C, during which adds the 1-methyl-2-pyrrolidinone of 70mL as dispersant,
Question response is filtered completely, is then placed in drying box at 100 DEG C dry 24h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The Raman collection of illustrative plates of class graphene molybdenum disulfide manufactured in the present embodiment is as shown in Figure 1, high-resolution SEM figure such as Fig. 2
It is shown.
E in Raman collection of illustrative plates in Fig. 12g 1With Ag 1Value is respectively 384.2 and 407.7, displacement difference 23.5, with reference to Raman spectral difference
Related article (Li H, Zhang Q, Yap C C R, the et al.From Bulk to of relation between value and the molybdenum disulfide number of plies
Monolayer MoS2:Evolution of Raman Scattering[J].Advanced Functional
Materials,2012,22(7):1385-1390.) understand, displacement difference is less than 25, and the number of plies of the product is 1~5 layer, belongs to few
Rotating fields molybdenum disulfide, that is, it is class graphene molybdenum disulfide to show sample prepared by the present embodiment.Fig. 2 middle high-resolutions SEM schemes
It is shown as the class graphene molybdenum disulfide of few layer.Comprehensive attached drawing can show that the sample prepared by the present embodiment is class graphene two
Molybdenum sulfide.
Embodiment 2：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 40g, sodium nitrate 5g, the concentrated sulfuric acid of mass concentration 98% be 300mL and
The hydrogen peroxide of mass concentration 30% is 60mL.
Then heating water bath at 10 DEG C and stirs 30min, carries out intercalation, be then heated to 95 to 10 DEG C of reaction 2h
DEG C stirring reaction 25min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 667mL's
Dimethylacetylamide, is reduction reaction 25min at 150 DEG C, during which adds the 1-methyl-2-pyrrolidinone of 67mL as dispersant,
Question response is filtered completely, is then placed in drying box at 110 DEG C dry 18h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 3：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 10g, sodium nitrate 8g, the concentrated sulfuric acid of mass concentration 98% be 400mL and
The hydrogen peroxide of mass concentration 30% is 45mL.
Then heating water bath at 45 DEG C and stirs 50min, carries out intercalation, be then heated to 98 to 30 DEG C of reaction 1h
DEG C stirring reaction 15min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 615mL's
Dimethylacetylamide, is reduction reaction 15min at 180 DEG C, and the polyvinylpyrrolidone for during which adding 62mL (selects polyethylene
Pyrrolidones is K.30) dispersant is used as, question response is filtered completely, is then placed in drying box at 120 DEG C dry 19h.
Drying goes out reaction product after taking, ground to obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 4：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 15g, sodium nitrate 20g, the concentrated sulfuric acid of mass concentration 98% be 210mL
Hydrogen peroxide with mass concentration 30% is 100mL.
Then heating water bath at 35 DEG C and stirs 20min, carries out intercalation, be then heated to 12 DEG C of reaction 2.5h
80 DEG C of stirring reaction 30min, resulting solution after reaction is filtered and dries filter cake, the sieving of 200 mesh is ground to, obtains intercalation two
Vulcanize molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 700mL's
Dimethylacetylamide, is reduction reaction 25min at 170 DEG C, during which adds the polyvinylpyrrolidone of 74mL as dispersant,
Question response is filtered completely, is then placed in drying box at 100 DEG C dry 20h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 5：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 35g, sodium nitrate 18g, the concentrated sulfuric acid of mass concentration 98% be 90mL and
The hydrogen peroxide of mass concentration 30% is 150mL.
Then heating water bath at 50 DEG C and stirs 20min, carries out intercalation, be then heated to 100 to 25 DEG C of reaction 3h
DEG C stirring reaction 10min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 750mL's
Dimethylacetylamide, is reduction reaction 40min at 150 DEG C, during which adds the 1-methyl-2-pyrrolidinone of 100mL as scattered
Agent, question response are filtered completely, are then placed in drying box at 120 DEG C dry 18h.Drying goes out reaction product after taking, and passes through
Grinding obtains class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 6：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 25g, sodium nitrate 15g, the concentrated sulfuric acid of mass concentration 98% be 150mL
Hydrogen peroxide with mass concentration 30% is 120mL.
Then heating water bath at 32 DEG C and stirs 25min, carries out intercalation, be then heated to 18 DEG C of reaction 2.5h
78 DEG C of stirring reaction 20min, resulting solution after reaction is filtered and dries filter cake, the sieving of 200 mesh is ground to, obtains intercalation two
Vulcanize molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 740mL's
Dimethylacetylamide, is reduction reaction 40min at 140 DEG C, during which adds the polyvinylpyrrolidone of 90mL as dispersant,
Question response is filtered completely, is then placed in drying box at 120 DEG C dry 18h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 7：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 30g, sodium nitrate 12g, the concentrated sulfuric acid of mass concentration 98% be 255mL
Hydrogen peroxide with mass concentration 30% is 65mL.
Then heating water bath at 42 DEG C and stirs 45min, carries out intercalation, be then heated to 20 DEG C of reaction 1.5h
88 DEG C of stirring reaction 12min, resulting solution after reaction is filtered and dries filter cake, the sieving of 200 mesh is ground to, obtains intercalation two
Vulcanize molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, reducing agent 1040mL
Dimethylformamide, be reduction reaction 20min at 160 DEG C, during which add the polyvinylpyrrolidone of 80mL as scattered
Agent, question response are filtered completely, are then placed in drying box at 120 DEG C dry 20h.Drying goes out reaction product after taking, and passes through
Grinding obtains class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 8：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 20g, sodium nitrate 10g, the concentrated sulfuric acid of mass concentration 98% be 225mL
Hydrogen peroxide with mass concentration 30% is 75mL.
Then heating water bath at 35 DEG C and stirs 20min, carries out intercalation, be then heated to 15 DEG C of reaction 2.5h
83 DEG C of stirring reaction 18min, resulting solution after reaction is filtered and dries filter cake, the sieving of 200 mesh is ground to, obtains intercalation two
Vulcanize molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 750mL's
Dimethylformamide, is reduction reaction 20min at 160 DEG C, during which adds the 1-methyl-2-pyrrolidinone of 75mL as dispersant,
Question response is filtered completely, is then placed in drying box at 120 DEG C dry 18h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 9：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 40g, sodium nitrate 5g, the concentrated sulfuric acid of mass concentration 98% be 300mL and
The hydrogen peroxide of mass concentration 30% is 60mL.
Then heating water bath at 38 DEG C and stirs 25min, carries out intercalation, be then heated to 86 to 12 DEG C of reaction 2h
DEG C stirring reaction 11min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 840mL's
Dimethylformamide, is reduction reaction 40min at 130 DEG C, during which adds the 1-methyl-2-pyrrolidinone of 63mL as dispersant,
Question response is filtered completely, is then placed in drying box at 120 DEG C dry 24h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 10：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 10g, sodium nitrate 8g, the concentrated sulfuric acid of mass concentration 98% be 400mL and
The hydrogen peroxide of mass concentration 30% is 45mL.
Then heating water bath at 70 DEG C and stirs 30min, carries out intercalation, be then heated to 25 DEG C of reaction 1.5h
90 DEG C of stirring reaction 22min, resulting solution after reaction is filtered and dries filter cake, the sieving of 200 mesh is ground to, obtains intercalation two
Vulcanize molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 835mL's
Dimethylformamide, is reduction reaction 20min at 160 DEG C, during which adds the 1-methyl-2-pyrrolidinone of 67mL as dispersant,
Question response is filtered completely, is then placed in drying box at 90 DEG C dry 21h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 11：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 15g, sodium nitrate 20g, the concentrated sulfuric acid of mass concentration 98% be 200mL
Hydrogen peroxide with mass concentration 30% is 100mL.
Then heating water bath at 60 DEG C and stirs 36min, carries out intercalation, be then heated to 96 to 20 DEG C of reaction 2h
DEG C stirring reaction 10min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 950mL's
Dimethylformamide, is reduction reaction 30min at 150 DEG C, during which adds the polyvinylpyrrolidone of 75mL as dispersant,
Question response is filtered completely, is then placed in drying box at 120 DEG C dry 18h.Drying goes out reaction product after taking, ground
Obtain class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Embodiment 12：
The present embodiment provides a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, and this method includes following step
Suddenly：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 35g, sodium nitrate 18g, the concentrated sulfuric acid of mass concentration 98% be 90mL and
The hydrogen peroxide of mass concentration 30% is 150mL.
Then heating water bath at 52 DEG C and stirs 42min, carries out intercalation, be then heated to 10 DEG C of reaction 2.5h
100 DEG C of stirring reaction 10min, resulting solution after reaction is filtered and dries filter cake, the sieving of 200 mesh is ground to, obtains intercalation
Molybdenum disulfide powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, reducing agent 1200mL
Dimethylformamide, be reduction reaction 30min at 150 DEG C, during which add the polyvinylpyrrolidone of 80mL as scattered
Agent, question response are filtered completely, are then placed in drying box at 100 DEG C dry 18h.Drying goes out reaction product after taking, and passes through
Grinding obtains class graphene molybdenum disulfide.
The characterization result of the present embodiment products therefrom class graphene molybdenum disulfide is substantially the same manner as Example 1.
Comparative example 1：
This comparative example provides a kind of method for preparing molybdenum disulfide, and this method comprises the following steps：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders, be added into
Mass concentration is 10%, in the ethanol solution containing 100g polyphenylene sulfides, and heating water bath is to 30 DEG C and stirs 12h, is mixed
Liquid.5gKMnO is added in above-mentioned mixed liquor4Powder, heating water bath is to 50 DEG C and stirs 18h, filters and dries filter cake, grinds
The sieving of 200 mesh is milled to, obtains intercalation molybdenum disulfide powder.
Step 2 is identical with the step of embodiment 1 two.
Step 3 is identical with the step of embodiment 1 three.
Raman spectrum analyses and sem analysis have been carried out to molybdenum disulfide made from this comparative example.Raman collection of illustrative plates such as Fig. 3
Shown, high-resolution SEM figures are as shown in Figure 4.Its characteristic peak E in Fig. 32g 1With Ag 1Value is respectively 375.3 and 402.5, and displacement difference is
27.2, displacement difference is more than 25, belongs to block structure molybdenum disulfide.The form of molybdenum disulfide shows this product molybdenum disulfide in Fig. 4
Block is accumulated, and sandwich construction is presented, and is not belonging to few layer molybdenum disulfide.
Comparative example 2：
This comparative example provides a kind of method for preparing molybdenum disulfide, and this method comprises the following steps：
Step 1, it is identical with other processes in the step of embodiment 1 one, differ only in：The composition of intercalation solution
The concentrated sulfuric acid for potassium permanganate 20g, sodium nitrate 10g, mass concentration 98% is 230mL.
Step 2 is identical with the step of embodiment 1 two.
Step 3 is identical with the step of embodiment 1 three.
There is the accumulation of molybdenum disulfide block as comparative example 1 in molybdenum disulfide made from this comparative example, is not belonging to class graphite
Alkene molybdenum disulfide.
Comparative example 3：
This comparative example provides a kind of method for preparing molybdenum disulfide, and this method comprises the following steps：
Step 1, is ground to the sieving of 200 mesh by molybdenum disulfide powder, takes 10g screenings molybdenum disulfide powders to be added to slotting
In layer solution, the composition of intercalation solution be potassium chlorate be 5g, sodium nitrate 15g, the concentrated sulfuric acid of mass concentration 98% be 375mL and
The hydrogen peroxide of mass concentration 30% is 50mL.
Then heating water bath at 40 DEG C and stirs 50min, carries out intercalation, be then heated to 50 to 18 DEG C of reaction 2h
DEG C stirring reaction 15min, by after reaction resulting solution filter and filter cake is dried, be ground to 200 mesh sieving, obtain two sulphur of intercalation
Change molybdenum powder.
Step 2, intercalation molybdenum disulfide powder 2g made from step 1 is added in reducing agent, and reducing agent is 265mL's
Dimethylacetylamide, is reduction reaction 50min at 120 DEG C, during which adds the polyvinylpyrrolidone of 10mL as dispersant,
Question response is filtered completely, is then placed in drying box at 80 DEG C dry 28h.Drying goes out reaction product after taking, ground
Obtain molybdenum disulfide.
Raman spectrum analyses and sem analysis are carried out to molybdenum disulfide made from this comparative example.Raman spectrum such as Fig. 5 institutes
Show, its E2g 1With Ag 1Value is respectively 384.7 and 410.2, and displacement difference 25.5, displacement difference is more than 25, belongs to block structure curing
Molybdenum.For SEM image as shown in fig. 6, illustrating that this product molybdenum disulfide block is accumulated, presentation sandwich construction, is not belonging to few layer curing
Molybdenum.
Claims (3)
1. a kind of method that low-temperature reduction prepares class graphene molybdenum disulfide, it is characterised in that this method comprises the following steps：
Step 1, molybdenum disulfide powder is added in intercalation solution and carries out intercalation, be heated to 10~30 DEG C reaction 1~
3h, then at 30~70 DEG C and stirs 20~50min, 10~30min of stirring reaction at 75~100 DEG C, filtering after the completion of reaction,
Drying, obtains intercalation molybdenum disulfide powder；
The mixed solution that the intercalation solution is potassium chlorate, sodium nitrate, the concentrated sulfuric acid and hydrogen peroxide form；The molybdenum disulfide
Powder and potassium chlorate, sodium nitrate, the concentrated sulfuric acid of mass concentration 98% and mass concentration 30% hydrogen peroxide between proportion relation
For 1g：(1~4) g：(0.5~2) g：(9~40) mL：(4~20) mL；
Step 2, intercalation molybdenum disulfide powder made from step 1 is added in reducing agent and carries out reduction reaction, and reaction 10~
40min, during which add dispersant, question response is complete, while hot with deionized water filter wash products, then 90 in drying box~
Dry 18~24h, class graphene molybdenum disulfide is obtained after grinding at 120 DEG C；
The reducing agent is dimethylformamide or dimethylacetylamide；The intercalation molybdenum disulfide powder and dimethyl methyl
Proportion relation between acid amides is 2g：(750~1200) mL；Between the intercalation molybdenum disulfide powder and dimethylacetylamide
Proportion relation be 2g：(615~750) mL；
The dispersant is 1-methyl-2-pyrrolidinone or polyvinylpyrrolidone；The intercalation molybdenum disulfide powder is with disperseing
Proportion relation between agent is 2g：(62~100) mL；
The reduction reaction temperature when dimethylformamide is as reducing agent is 130~160 DEG C, the dimethylacetamide
Reduction reaction temperature when amine is as reducing agent is 140~180 DEG C.
2. the method as described in claim 1, it is characterised in that the molybdenum disulfide powder and potassium chlorate, sodium nitrate, quality
Proportion relation between the concentrated sulfuric acid of concentration 98% and the hydrogen peroxide of mass concentration 30% is 1g：2g：1g：23mL：7mL.
3. the method as described in claim 1, it is characterised in that the intercalation molybdenum disulfide powder and dimethylacetylamide it
Between proportion relation be 2g：700mL.
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| CN105668631A (en) * | 2016-03-14 | 2016-06-15 | 西安建筑科技大学 | Preparing method of single-layer or few-layer molybdenum disulfide nanometer material |
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| CN104973593A (en) * | 2015-06-18 | 2015-10-14 | 湖南大学 | Stripping method of stratified materials |
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