CN106335927A - Method for preparing 2H phase single layer tungsten disulfide nano sheet - Google Patents
Method for preparing 2H phase single layer tungsten disulfide nano sheet Download PDFInfo
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- CN106335927A CN106335927A CN201610698730.2A CN201610698730A CN106335927A CN 106335927 A CN106335927 A CN 106335927A CN 201610698730 A CN201610698730 A CN 201610698730A CN 106335927 A CN106335927 A CN 106335927A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The present invention discloses a method for preparing a 2H phase single layer tungsten disulfide nano sheet, and specific steps are as follows: ammonium thiotungstate and a lithium salt compound are mixed and according to the molar ratio of 1:2, a ground mixture is kept warm at 200-600 DEG C for 1-10h under the protection of an inert gas, then cooled to room temperature to obtain a lithium-intercalated 2H phase tungsten sulfide block; the lithium-intercalated 2H phase tungsten sulfide block is put into deionized water for assisted ultrasonic hydrolysis separating for 5-30min, an obtained suspension is put into a centrifuge for centrifugal separation for removal of unstripped precipitates to obtain a 2H phase monolayer WS2 nano sheet suspension; water and ethanol are respectively used to remove soluble impurities in the 2H phase monolayer WS2 nano sheet suspension by the centrifuge, finally precipitate 2H phase monolayer WS2 nano sheets are dispersed in a small molecule solvent for preservation, and the thickness of the 2H phase monolayer WS2 nano sheets is less than 1nm. The method has the advantages of being simple in process operation, mild in reaction condition, low in price of reagents, green and environmentally-friendly.
Description
Technical field
The invention belongs to the synthesis technical field of Wolfram disulfide nano material is and in particular to a kind of 2h phase individual layer tungsten disulfide
The preparation method of nanometer sheet.
Background technology
Tungsten disulfide is identical with molybdenum bisuphide structure, is all typical sandwich layer structure, because its interlayer is relatively weak
Van der Waals force it is also possible to peel off into the nanometer sheet of individual layer or few number of plies it is considered to be another considerable two wiener
Rice sheet material, has unique physics, chemically and electrically characteristic.Tungsten disulfide is identical with molybdenum bisuphide, all there are three kinds of phases,
I.e. 1t, 2h and 3r phase, wherein, 1t phase is ws2Stacked using a s-w-s monolayer as minimum repetitive, and 2h and 3r
It is mutually to be stacked using two and three s-w-s monolayers as minimum repetitive.Most of ws in nature2It is stable with 2h
Mutually exist, 1t with 3r phase belongs to metastable structure, 2h phase can be changed under certain condition.Ws due to individual layer 2h phase2
Have been out the characteristic that bilayer is minimum repetitive, therefore also referred to as 1h phase.The ws of different phases2Material institute
The physicochemical characteristics presenting also is not quite similar.For example, 2h state material represents characteristic of semiconductor, and the ws of 1t state2Material is in then
Reveal metallic character.Although individual layer ws2Nano material heat, the property of the aspect such as electricity, light, mechanics and its opto-electronic device neck
The potential application in domain causes the extensive concern of scientific research personnel.However, general chemistry, Physical are difficult to prepare pure individual layer knot
The ws of structure2The individual layer tungsten sulfide of nano material, especially different phase peels off preparation.Synthesis about tungsten disulfide at present and should
It is ws with report major part2Nanometer sheet, ws2Nanometer rods and ws2Compound with carbon fiber and Graphene etc..For example: application number
Patent for 201510975198.x discloses a kind of preparation method of graphite-like tungsten disulfide nano slices；Application No.
201610008800.7 patent disclose a kind of tungsten sulfide nanometer rods preparation method；Application No. 201310533441.3 special
Profit discloses class Graphene tungsten disulfide nano slices preparation method；The patent of Application No. 201510622958.9 discloses one kind
The preparation method of tungsten sulfide/carbon nano-fiber/graphene complex；The patent of Application No. 201410065185.4 discloses one
Plant Wolfram disulfide nano preparation of sections method.Although the Wolfram disulfide nano material of these methods synthesis is in certain dimension direction
On be nanoscale, but be not individual layer tungsten disulfide, presently disclosed documents and materials are nearly no in addition individual layer tungsten disulfide
Relevant report, the preparation of the individual layer tungsten disulfide nano slices of especially single specified phase.
Content of the invention
Present invention solves the technical problem that there is provided a kind of 2h phase of simple, safe efficient and suitable large-scale production
The preparation method of individual layer tungsten disulfide nano slices, the method is with thio ammonium tungstate and lithium salt compound as raw material, in a constant temperature
It is thermally treated resulting in the slotting lithium li of 2h phase under degree2ws2Block, slotting lithium li2ws2Block hydrolyzes in deionized water voluntarily to peel off and obtains
Single target product.
The present invention is that solution above-mentioned technical problem adopts the following technical scheme that, a kind of 2h phase individual layer tungsten disulfide nano slices
Preparation method is it is characterised in that concretely comprise the following steps:
(1) thio ammonium tungstate and lithium salt compound are pressed 1:2 mixed in molar ratio to grind, the mixture after grinding is protected in inert gas
It is incubated 1-10h in 200-600 DEG C under shield, be cooled to room temperature and obtain inserting the 2h phase tungsten sulfide block of lithium；
(2) the 2h phase tungsten sulfide block of slotting lithium is placed directly within deionized water, 5-30min is peeled off in assisting ultrasonic hydrolysis, then will
The suspension obtaining is placed in a centrifuge, and obtains 2h phase individual layer ws after being centrifuged removing unstripped sediment2Nanometer sheet
Suspension；
(3) by 2h phase individual layer ws2Nanometer sheet suspension uses water and the removal of ethanol centrifuge washing soluble miscellaneous on centrifuge respectively
Matter, finally by sediment 2h phase individual layer ws2Nanometer sheet is scattered in small molecule solvent and preserves, this 2h phase individual layer ws2The thickness of nanometer sheet
Degree is less than 1nm.
Limit further, the lithium salt compound described in step (1) be lithium hydroxide, lithium chloride, lithium acetate, lithium carbonate,
One or more of lithium sulfate or lithium nitrate.
Limit further, the centrifuge speed described in step (2) is 1000r/min, the centrifuge described in step (3)
Rotating speed is 4000-20000r/min.
Limit further, the small molecule solvent described in step (3) be water, methyl alcohol, ethanol, isopropanol, butanol, acetone,
N- methyl pyrrolidone or n- NMF.
The present invention compared with prior art has the advantage that
1st, the present invention, with thio ammonium tungstate and lithium salt compound as raw material, can synthesize slotting lithium by simple temperature control
2h phase tungsten sulfide block, the 2h phase tungsten sulfide block of slotting lithium can hydrolyze in water voluntarily peels off into 2h phase individual layer ws2Nanometer sheet,
And can in the small molecule solvents such as water, ethanol stable existence；
2nd, the 2h phase individual layer ws that the present invention obtains2The thickness of nanometer sheet is less than 1nm, rather than 1-100nm thickness of the prior art
Ws2Nanometer sheet；
3rd, the 2h phase individual layer ws of present invention synthesis2Nanometer sheet can be used for individual layer tungsten sulfide in light liberation of hydrogen, electro-catalysis and energy storage etc.
The research in field；
4th, present invention process is simple to operate, and reaction condition is gentle, and agents useful for same is cheap, environmental protection.
Specific embodiment
By the following examples the above of the present invention is described in further details, but this should not be interpreted as this
The scope inventing above-mentioned theme is only limitted to below example, all belongs to this based on the technology that the above of the present invention is realized
Bright scope.
Embodiment 1
Weigh the lithium hydroxide of 0.004mol and the thio ammonium tungstate of 0.002mol respectively, mixed grinding 1h in agate mortar,
Mixture after grinding is placed in corundum crucible, is placed in tube furnace, logical argon gas protection, temperature programming, to 600 DEG C, is incubated
1h, then proceedes to logical argon gas and is naturally cooling to room temperature, obtain inserting the 2h phase tungsten sulfide (li of lithium2ws4) block；Sulfuration by slotting lithium
Tungsten block is placed in the container filling 50ml deionized water, ultrasonic disperse 10min, and the suspension after dispersion is 1000r/ in rotating speed
Centrifugation precipitation on the centrifuge of min；The difference on rotating speed is for the centrifuge of 4000r/min of the suspension after precipitation will be removed
With water and 3 removal li of ethanol centrifuge washing2The soluble impurities such as s, by washing after sediment ultrasonic disperse 100ml go from
In sub- water, wherein 2h phase individual layer ws2Concentration be about 0.6mg/ml, through AFM detect its thickness be 0.75nm, x-
Photoelectron spectroscopy is shown as 2h phase.
Embodiment 2
Weigh the lithium acetate of 0.004mol and the thio ammonium tungstate of 0.002mol, mixed grinding 1h in agate mortar respectively, incite somebody to action
Mixture after grinding is placed in corundum crucible, is placed in tube furnace, logical argon gas protection, and temperature programming, to 200 DEG C, is incubated
10h, then proceedes to logical argon gas and is naturally cooling to room temperature, obtain inserting the 2h phase tungsten sulfide (li of lithium2ws4) block；Sulfuration by slotting lithium
Tungsten block is placed in the container filling 50ml deionized water, ultrasonic disperse 10min, and the suspension after dispersion is 1000r/ in rotating speed
Centrifugation precipitation on the centrifuge of min；By remove precipitation after suspension in rotating speed for 10000r/min with centrifuge
Use water and 3 removal li of ethanol centrifuge washing respectively2The soluble impurities such as s, by the sediment ultrasonic disperse after washing in 100ml
In absolute ethyl alcohol, wherein 2h phase individual layer ws2Concentration be about 0.8mg/ml, detect that its thickness is through AFM
0.80nm, x- photoelectron spectroscopy is shown as 2h phase.
Embodiment 3
Weigh the lithium nitrate of 0.004mol and the thio ammonium tungstate of 0.002mol, mixed grinding 1h in agate mortar respectively, incite somebody to action
Mixture after grinding is placed in corundum crucible, is placed in tube furnace, logical argon gas protection, and temperature programming, to 300 DEG C, is incubated
5h, then proceedes to logical argon gas and is naturally cooling to room temperature, obtain inserting the 2h phase tungsten sulfide (li of lithium2ws4) block；Sulfuration by slotting lithium
Tungsten block is placed in the container filling 50ml deionized water, ultrasonic disperse 5min, and the suspension after dispersion is 1000r/ in rotating speed
Centrifugation precipitation on the centrifuge of min；Divide removing the suspension after precipitation on rotating speed is for the centrifuge of 15000r/min
Yong not water and 3 removal li of ethanol centrifuge washing2The soluble impurities such as s, will be different in 100ml for the sediment ultrasonic disperse after washing
In propyl alcohol, wherein 2h phase individual layer ws2Concentration be about 1.1mg/ml, through AFM detect its thickness be 0.68nm, x-
Photoelectron spectroscopy is shown as 2h phase.
Embodiment 4
Weigh the lithium carbonate of 0.004mol and the thio ammonium tungstate of 0.002mol, mixed grinding 1h in agate mortar respectively, grind
Mixture being placed in corundum crucible after mill, is placed in tube furnace, logical argon gas protection, and temperature programming, to 300 DEG C, is incubated
5h, then proceedes to logical argon gas and is naturally cooling to room temperature, obtain inserting the 2h phase tungsten sulfide (li of lithium2ws4) block；Sulfuration by slotting lithium
Tungsten block is placed in the container filling 50ml deionized water, ultrasonic disperse 30min, and the suspension after dispersion is 1000r/ in rotating speed
Centrifugation precipitation on the centrifuge of min；The centrifuge difference in rotating speed for 20000r/min for the suspension after precipitation will be removed
With water and 3 removal li of ethanol centrifuge washing2The soluble impurities such as s, by the sediment ultrasonic disperse after washing in 100ml n-
In methyl pyrrolidone, wherein 2h phase individual layer ws2Concentration be about 1.2mg/ml, detect that its thickness is through AFM
0.65nm, x- photoelectron spectroscopy is shown as 2h phase.
Embodiment above describes general principle, principal character and the advantage of the present invention, the technical staff of the industry should
Understand, the present invention is not restricted to the described embodiments, the simply explanation present invention's described in above-described embodiment and specification is former
Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (4)
1. a kind of preparation method of 2h phase individual layer tungsten disulfide nano slices is it is characterised in that concretely comprise the following steps:
(1) thio ammonium tungstate and lithium salt compound are pressed 1:2 mixed in molar ratio to grind, the mixture after grinding is protected in inert gas
It is incubated 1-10h in 200-600 DEG C under shield, be cooled to room temperature and obtain inserting the 2h phase tungsten sulfide block of lithium；
(2) the 2h phase tungsten sulfide block of slotting lithium is placed directly within deionized water, 5-30min is peeled off in assisting ultrasonic hydrolysis, then will
The suspension obtaining is placed in a centrifuge, and obtains 2h phase individual layer ws after being centrifuged removing unstripped sediment2Nanometer sheet
Suspension；
(3) by 2h phase individual layer ws2Nanometer sheet suspension uses water and the removal of ethanol centrifuge washing soluble miscellaneous on centrifuge respectively
Matter, finally by sediment 2h phase individual layer ws2Nanometer sheet is scattered in small molecule solvent and preserves, this 2h phase individual layer ws2The thickness of nanometer sheet
Degree is less than 1nm.
2. 2h phase individual layer tungsten disulfide nano slices according to claim 1 preparation method it is characterised in that: step (1)
Described in lithium salt compound be one of lithium hydroxide, lithium chloride, lithium acetate, lithium carbonate, lithium sulfate or lithium nitrate or many
Kind.
3. 2h phase individual layer tungsten disulfide nano slices according to claim 1 preparation method it is characterised in that: step (2)
Described in centrifuge speed be 1000r/min, the centrifuge speed described in step (3) be 4000-20000r/min.
4. 2h phase individual layer tungsten disulfide nano slices according to claim 1 preparation method it is characterised in that: step (3)
Described in small molecule solvent be water, methyl alcohol, ethanol, isopropanol, butanol, acetone, n- methyl pyrrolidone or n- methyl formyl
Amine.
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| CN201610698730.2A CN106335927B (en) | 2016-08-22 | 2016-08-22 | A kind of preparation method of 2H phases individual layer tungsten disulfide nano slices |
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| CN201610698730.2A CN106335927B (en) | 2016-08-22 | 2016-08-22 | A kind of preparation method of 2H phases individual layer tungsten disulfide nano slices |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174128A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | A kind of method of modifying of tungsten disulfide and its application |
| CN109374710A (en) * | 2018-10-30 | 2019-02-22 | 浙江大学 | A kind of all solid state ion selective electrode and preparation method thereof based on conductive tungsten disulfide nano slices modified electrode |
| CN113023780A (en) * | 2021-03-17 | 2021-06-25 | 李伟强 | Nanoscale tungsten disulfide material, preparation method and preparation device thereof |
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| CN103480856A (en) * | 2013-09-09 | 2014-01-01 | 南京邮电大学 | Method for preparing nanocomposite by using two-dimensional transition metal chalcogenide nanosheets and metal |
| CN105293580A (en) * | 2015-10-15 | 2016-02-03 | 南京大学 | Method for preparing dispersion liquid of two-dimensional nano-sheet layer of transition metal sulfide |
| CN105668530A (en) * | 2016-01-14 | 2016-06-15 | 苏州微格纳米科技有限公司 | Preparation method of two-dimensional nanomaterial |
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- 2016-08-22 CN CN201610698730.2A patent/CN106335927B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480856A (en) * | 2013-09-09 | 2014-01-01 | 南京邮电大学 | Method for preparing nanocomposite by using two-dimensional transition metal chalcogenide nanosheets and metal |
| CN105293580A (en) * | 2015-10-15 | 2016-02-03 | 南京大学 | Method for preparing dispersion liquid of two-dimensional nano-sheet layer of transition metal sulfide |
| CN105668530A (en) * | 2016-01-14 | 2016-06-15 | 苏州微格纳米科技有限公司 | Preparation method of two-dimensional nanomaterial |
Non-Patent Citations (1)
| Title |
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| HUI-LIEN TSAI ET AL.: "Exfoliated-Restacked Phase of WS2", 《CHEM. MATER》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174128A (en) * | 2018-09-13 | 2019-01-11 | 浙江大学 | A kind of method of modifying of tungsten disulfide and its application |
| CN109374710A (en) * | 2018-10-30 | 2019-02-22 | 浙江大学 | A kind of all solid state ion selective electrode and preparation method thereof based on conductive tungsten disulfide nano slices modified electrode |
| CN109374710B (en) * | 2018-10-30 | 2020-08-04 | 浙江大学 | Conductive tungsten disulfide nanosheet-based modified ion selective electrode and preparation method thereof |
| CN113023780A (en) * | 2021-03-17 | 2021-06-25 | 李伟强 | Nanoscale tungsten disulfide material, preparation method and preparation device thereof |
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