CN106315678B - A kind of preparation method of 1T phases individual layer tungsten disulfide nano slices - Google Patents
A kind of preparation method of 1T phases individual layer tungsten disulfide nano slices Download PDFInfo
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- CN106315678B CN106315678B CN201610698729.XA CN201610698729A CN106315678B CN 106315678 B CN106315678 B CN 106315678B CN 201610698729 A CN201610698729 A CN 201610698729A CN 106315678 B CN106315678 B CN 106315678B
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Abstract
The invention discloses a kind of preparation method of 1T phases individual layer tungsten disulfide nano slices, concretely comprise the following steps：Thio ammonium tungstate and lithium salt compound are pressed 1:2 mixed in molar ratio are ground, and the mixture after grinding is incubated 1 10h under inert gas shielding in 800 1300 DEG C, are cooled to the 1T phase tungsten sulfide blocks that room temperature obtains inserting lithium；The 1T phase tungsten sulfide blocks of slotting lithium are placed in deionized water, 5 30min are peeled off in assisting ultrasonic hydrolysis, then obtained suspension is placed in a centrifuge, are centrifuged obtaining 1T phase individual layers WS after removing unstripped sediment2Nanometer sheet suspension；By 1T phase individual layers WS2Nanometer sheet suspension removes soluble impurity with water and ethanol centrifuge washing respectively on centrifuge, finally by sediment 1T phase individual layers WS2Nanometer sheet, which is scattered in small molecule solvent, to be preserved, 1T phase individual layers WS2The thickness of nanometer sheet is less than 1nm.Present invention process is simple to operate, and reaction condition is gentle, and agents useful for same is cheap, environmental protection.
Description
Technical field
The invention belongs to the synthesis technical field of Wolfram disulfide nano material, and in particular to a kind of 1T phases individual layer tungsten disulfide
The preparation method of nanometer sheet.
Background technology
Tungsten disulfide is identical with molybdenum disulfide structure, is all typical sandwich layer structure, because its interlayer is relatively weak
Van der Waals force, the nanometer sheet of individual layer or few number of plies can also be peeled off into, it is considered to be another considerable two wiener
Rice sheet material, with unique physics, chemically and electrically characteristic.Tungsten disulfide is identical with molybdenum disulfide, all in the presence of three kinds of phases,
That is 1T, 2H and 3R phase, wherein, 1T phases are WS2Stacked using a S-W-S monolayer as minimum repeat unit, and 2H and 3R
It is mutually to be stacked using two and three S-W-S monolayers as minimum repeat unit.Major part WS in nature2It is stable with 2H
Mutually exist, 1T with 3R phases belong to metastable structure, can be changed into 2H phases under certain condition.Due to the WS of individual layer 2H phases2
The characteristic that bilayer is minimum repeat unit, therefore also referred to as 1H phases are lost.The WS of different phases2Material institute
The physicochemical characteristics of presentation is also not quite similar.For example, 2H state materials show characteristic of semiconductor, and the WS of 1T states2Material is in then
Reveal metallic character.Although individual layer WS2Property of the nano material in terms of heat, electricity, light, mechanics and its in 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, which is peeled off, to be prepared.The synthesis of relevant tungsten disulfide at present and answer
Most of with report is WS2Nanometer sheet, WS2Nanometer rods and WS2With the compound of carbon fiber and graphene etc..For example：Application number
A kind of preparation method of graphite-like tungsten disulfide nano slices is disclosed for 201510975198.X patent；Application No.
201610008800.7 patent disclose a kind of tungsten sulfide nanometer rods preparation method；Application No. 201310533441.3 it is 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.The Wolfram disulfide nano material of these methods synthesis is although in some 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.
The content of the invention
Present invention solves the technical problem that there is provided a kind of 1T phases of simple, safe efficient and suitable large-scale production
The preparation method of individual layer tungsten disulfide nano slices, this method is using thio ammonium tungstate and lithium salt compound as raw material, in a constant temperature
The slotting lithium Li of 1T phases is thermally treated resulting under degree2WS2Block, inserts lithium Li2WS2Block is hydrolyzed voluntarily to peel off in deionized water and obtained
Single target product.
Wei Xie Decision above-mentioned technical problems of the present invention adopt the following technical scheme that, a kind of 1T phases individual layer tungsten disulfide nano slices
Preparation method, 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 are ground, and the mixture after grinding is in indifferent gas
1-10h is incubated in 800-1300 DEG C under body protection, the 1T phase tungsten sulfide blocks that room temperature obtains inserting lithium are cooled to；
（2）The 1T phase tungsten sulfide blocks of slotting lithium are placed directly within deionized water, 5-30min is peeled off in assisting ultrasonic hydrolysis,
Obtained suspension is placed in a centrifuge again, is centrifuged obtaining 1T phase individual layers WS after removing unstripped sediment2Receive
Rice piece suspension；
（3）By 1T phase individual layers WS2Nanometer sheet suspension is solvable with water and the removal of ethanol centrifuge washing respectively on centrifuge
Property impurity, finally by sediment 1T phase individual layers WS2Nanometer sheet, which is scattered in small molecule solvent, to be preserved, 1T phase individual layers WS2Nanometer sheet
Thickness be less than 1nm.
Further limit, step（1）Described in lithium salt compound for lithium hydroxide, lithium chloride, lithium acetate, lithium carbonate,
One or more in lithium sulfate or lithium nitrate.
Further limit, step（2）Described in centrifuge speed be 1000r/min, step（3）Described in centrifuge
Rotating speed is 4000-20000r/min.
Further limit, step（3）Described in small molecule solvent for water, methanol, ethanol, isopropanol, butanol, acetone,
1-METHYLPYRROLIDONE or N-METHYLFORMAMIDE.
The present invention has advantages below compared with prior art：
1st, the present invention can be synthesized slotting using thio ammonium tungstate and lithium salt compound as raw material by simple temperature control
The 1T phase tungsten sulfide blocks of lithium, the 1T phase tungsten sulfides block of slotting lithium can be hydrolyzed in water voluntarily peels off into 1T phase individual layers WS2Receive
Rice piece, and can be stabilized in the small molecule solvents such as water, ethanol；
2nd, the 1T phase individual layers WS that the present invention is obtained2The thickness of nanometer sheet is less than 1nm, rather than 1-100nm of the prior art
The WS of thickness2Nanometer sheet；
3rd, the 1T phase individual layers WS that the present invention is synthesized2Nanometer sheet can be used for individual layer tungsten sulfide in light liberation of hydrogen, electro-catalysis and storage
The research in the fields such as energy；
4th, present invention process is simple to operate, and reaction condition is gentle, and agents useful for same is cheap, environmental protection.
Embodiment
The above to the present invention is described in further details by the following examples, but this should not be interpreted as to this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
0.004mol lithium hydroxide and 0.002mol thio ammonium tungstate, the mixed grinding in agate mortar are weighed respectively
1h, the mixture after grinding is placed in corundum crucible, is placed in tube furnace, lead to argon gas protection, temperature programming to 800 DEG C,
10h is incubated, logical argon gas is then proceeded to and is naturally cooling to room temperature, obtain inserting the 1T phase tungsten sulfides of lithium（Li2WS4）Block；By slotting lithium
Tungsten sulfide block is placed in the container for filling 50mL deionized waters, ultrasonic disperse 10min, and the suspension after disperseing is in rotating speed
Precipitation is centrifuged on 1000r/min centrifuge；The suspension after precipitation will be removed in the centrifuge that rotating speed is 4000r/min
It is upper to use 3 removal Li of water and ethanol centrifuge washing respectively2The soluble impurities such as S, the sediment ultrasonic disperse after washing is existed
In 100mL deionized waters, wherein 1T phases individual layer WS2Concentration be about 0.6mg/mL, detect that its thickness is through AFM
0.76nm, X- photoelectron spectroscopy are shown as 1T phases.
Embodiment 2
0.004mol lithium acetate and 0.002mol thio ammonium tungstate, the mixed grinding in agate mortar are weighed respectively
1h, the mixture after grinding is placed in corundum crucible, is placed in tube furnace, lead to argon gas protection, temperature programming to 1300 DEG C,
1T is incubated, logical argon gas is then proceeded to and is naturally cooling to room temperature, obtain inserting the 1T phase tungsten sulfides of lithium（Li2WS4）Block；By slotting lithium
Tungsten sulfide block is placed in the container for filling 50mL deionized waters, ultrasonic disperse 10min, and the suspension after disperseing is in rotating speed
Precipitation is centrifuged on 1000r/min centrifuge；To remove the suspension after precipitation rotating speed for 10000r/min with from
Respectively with 3 removal Li of water and ethanol centrifuge washing in scheming2The soluble impurities such as S, by the sediment ultrasonic disperse after washing
In 100mL absolute ethyl alcohols, wherein 1T phases individual layer WS2Concentration be about 0.8mg/mL, detect its thickness through AFM
For 0.70nm, X- photoelectron spectroscopies are shown as 1T phases.
Embodiment 3
0.004mol lithium nitrate and 0.002mol thio ammonium tungstate, the mixed grinding in agate mortar are weighed respectively
1h, the mixture after grinding is placed in corundum crucible, is placed in tube furnace, lead to argon gas protection, temperature programming to 1000 DEG C,
5h is incubated, logical argon gas is then proceeded to and is naturally cooling to room temperature, obtain inserting the 1T phase tungsten sulfides of lithium（Li2WS4）Block；By slotting lithium
Tungsten sulfide block is placed in the container for filling 50mL deionized waters, ultrasonic disperse 5min, and the suspension after disperseing is in rotating speed
Precipitation is centrifuged on 1000r/min centrifuge；The suspension after precipitation will be removed in the centrifugation that rotating speed is 15000r/min
Respectively with 3 removal Li of water and ethanol centrifuge washing on machine2The soluble impurities such as S, the sediment ultrasonic disperse after washing is existed
In 100mL isopropanols, wherein 1T phases individual layer WS2Concentration be about 1.0mg/mL, detect that its thickness is through AFM
0.75nm, X- photoelectron spectroscopy are shown as 1T phases.
Embodiment 4
0.004mol lithium carbonate and 0.002mol thio ammonium tungstate, the mixed grinding in agate mortar are weighed respectively
1h, mixture is placed in corundum crucible after grinding, is placed in tube furnace, lead to argon gas protection, temperature programming to 900 DEG C,
5h is incubated, logical argon gas is then proceeded to and is naturally cooling to room temperature, obtain inserting the 1T phase tungsten sulfides of lithium（Li2WS4）Block；By slotting lithium
Tungsten sulfide block is placed in the container for filling 50mL deionized waters, ultrasonic disperse 30min, and the suspension after disperseing is in rotating speed
Precipitation is centrifuged on 1000r/min centrifuge；The suspension after precipitation will be removed in the centrifugation that rotating speed is 20000r/min
Machine is respectively with 3 removal Li of water and ethanol centrifuge washing2The soluble impurities such as S, the sediment ultrasonic disperse after washing is existed
In 100mL 1-METHYLPYRROLIDONEs, wherein 1T phases individual layer WS2Concentration be about 1.2mg/mL, detect it through AFM
Thickness is 0.70nm, and X- photoelectron spectroscopies are shown as 1T phases.
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 limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. a kind of preparation method of 1T phases individual layer tungsten disulfide nano slices, 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 are ground, and the mixture after grinding is protected in inert gas
1-10h is incubated in 800-1300 DEG C under shield, the 1T phase tungsten sulfide blocks that room temperature obtains inserting lithium, described lithium salt compound is cooled to
For the one or more in lithium hydroxide, lithium chloride, lithium acetate, lithium carbonate, lithium sulfate or lithium nitrate；
（2）The 1T phase tungsten sulfide blocks of slotting lithium are placed directly within deionized water, 5-30min is peeled off in assisting ultrasonic hydrolysis, then will
Obtained suspension is placed in a centrifuge, and is centrifuged obtaining 1T phase individual layers WS after removing unstripped sediment2Nanometer sheet
Suspension；
（3）By 1T phase individual layers WS2Nanometer sheet suspension is soluble miscellaneous with water and the removal of ethanol centrifuge washing respectively on centrifuge
Matter, finally by sediment 1T phase individual layers WS2Nanometer sheet, which is scattered in small molecule solvent, to be preserved, 1T phase individual layers WS2The thickness of nanometer sheet
Degree is less than 1nm, and described small molecule solvent is water, methanol, ethanol, isopropanol, butanol, acetone, 1-METHYLPYRROLIDONE or N-
NMF.
2. the preparation method of 1T phases individual layer tungsten disulfide nano slices according to claim 1, it is characterised in that：Step（2）
Described in centrifuge speed be 1000r/min, step（3）Described in centrifuge speed be 4000-20000r/min.
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| CN108080005B (en) * | 2017-11-13 | 2020-05-26 | 西安交通大学 | Preparation method of 1T' phase tungsten sulfide of high-catalytic-activity electrocatalyst |
| 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 |
| CN111477716B (en) * | 2020-04-14 | 2021-07-27 | 合肥工业大学 | 1T-phase tungsten sulfide bipolar heterojunction narrow-band near-infrared photoelectric detector and preparation method thereof |
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| CN103771521B (en) * | 2014-02-26 | 2015-02-25 | 新疆大学 | Method for preparing tungsten disulfide nano sheet |
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