CN112939082A - Green, low-cost and efficient transition metal disulfide nanosheet preparation method - Google Patents
Green, low-cost and efficient transition metal disulfide nanosheet preparation method Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 15
- -1 transition metal disulfide Chemical class 0.000 title claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 103
- 229920002678 cellulose Polymers 0.000 claims abstract description 62
- 239000001913 cellulose Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 14
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229920000742 Cotton Polymers 0.000 claims abstract description 7
- 239000002159 nanocrystal Substances 0.000 claims description 41
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000000502 dialysis Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical group S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000004299 exfoliation Methods 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 229910003090 WSe2 Inorganic materials 0.000 description 8
- 229910052961 molybdenite Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000007865 diluting Methods 0.000 description 6
- 238000002525 ultrasonication Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000000554 physical therapy Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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Abstract
The invention belongs to the technical field of materials, and particularly relates to a green, low-cost and efficient preparation method of a transition metal disulfide nanosheet. Firstly, hydrolyzing cotton paper pulp by a sulfuric acid hydrolysis method to prepare cellulose nanocrystalline dispersion liquid with a certain length-diameter ratio, mixing transition metal disulfide powder and cellulose nanocrystalline in a certain proportion, then carrying out ultrasonic treatment in a water phase by using an ultrasonic instrument to complete a stripping process, and finally centrifuging the stripped dispersion liquid to remove the non-stripped part, thus obtaining the two-dimensional transition metal disulfide nanosheet dispersion liquid with ultrahigh concentration and stable dispersion in water.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a green, low-cost and efficient preparation method of a transition metal disulfide nanosheet.
Background
The development of some high-performance two-dimensional nano materials has become the focus of the development of new materials at the front edge, wherein the high-performance two-dimensional nano materials comprise graphene and transition metal disulfide nano Sheets (TMDs) (WS)2、MoS2、MoSe2And WSe2Etc.). The transition metal disulfide has excellent comprehensive properties such as high specific surface area, special energy band structure, nanosheet morphology and the like, and is widely concerned by people in the fields of flexible sensing, energy storage catalysis, photothermal physiotherapy, engineering materials, tissue engineering, biological imaging and the like.
The existing TMDs preparation methods comprise mechanical stripping, lithium ion intercalation, chemical vapor deposition, wet chemical methods and the like, and the methods have the problems of high pollution, low stripping efficiency, complicated steps, difficulty in large-scale production and the like. Compared with the preparation methods, the method for carrying out liquid phase ultrasonic stripping by taking the biomass-based macromolecules as the auxiliary stripping reagent has the advantages of simplicity, easiness in large-scale production and the like. Although some researchers at present use sodium alginate, chitin, cellulose nanofibers, bovine serum albumin, DNA and other biomass materials as auxiliary stripping reagents to carry out ultrasonic stripping on TMDS nanosheets, the obtained transition metal disulfide nanosheets are often relatively low in concentration, and meanwhile, the auxiliary stripping reagents are relatively low in cost, so that the low-cost and high-concentration large-scale preparation of TMDS is still a challenge, and the industrial application step of TMDS is greatly hindered. The application provides a low-cost and widely-available Cellulose Nanocrystalline (CNC) as an auxiliary stripping reagent, and TMDS nanosheets with ultrahigh concentration and stable dispersion in water are efficiently obtained by a simple liquid-phase ultrasonic stripping method.
Disclosure of Invention
The invention provides a green, low-cost and efficient preparation method of a transition metal disulfide nanosheet. The method adopts a traditional sulfuric acid hydrolysis route to prepare the cellulose nanocrystalline, then carries out ultrasonic treatment on TMDS powder and the cellulose nanocrystalline, and finally obtains the high-concentration TMDS nanosheet dispersion liquid through centrifugation.
The method specifically comprises the following steps:
firstly, hydrolyzing cotton paper pulp by a sulfuric acid hydrolysis method to prepare cellulose nanocrystalline dispersion liquid with a certain length-diameter ratio, mixing transition metal disulfide powder and cellulose nanocrystalline in a certain proportion, then carrying out ultrasonic treatment in a water phase by using an ultrasonic instrument to complete a stripping process, and finally centrifuging the stripped dispersion liquid to remove the non-stripped part, thereby obtaining the two-dimensional transition metal disulfide nanosheet dispersion liquid with ultrahigh concentration and stable dispersion in water.
A green, low-cost and efficient preparation method of a transition metal disulfide nanosheet specifically comprises the following steps:
mixing the cellulose nanocrystal dispersion liquid with TMDS powder, and then carrying out ultrasonic treatment and centrifugation to obtain a supernatant, namely the final TMDS nanosheet dispersion liquid;
the mass ratio of the cellulose nanocrystals to the TMDS powder in the cellulose nanocrystal dispersion liquid is as follows: (0.5-3): 1, preferably 2: 1.
further, the concentration of the cellulose nanocrystal dispersion is 10-50mg/mL, preferably 20 mg/mL.
Further, the ultrasound is performed for 20-50h under 250W, and more preferably for 30 h.
Further, the TMDs powder is tungsten disulfide, molybdenum disulfide, or tungsten diselenide powder.
Further, the size of the TMDs powder is 25-50 μm.
Further, the preparation method of the cellulose nanocrystal dispersion comprises the following steps:
(1) pretreating the cotton paper pulp by using a sodium hydroxide solution, then carrying out suction filtration and washing to be neutral, and drying to obtain paper pulp;
(2) adding the paper pulp obtained in the step (1) into a reaction vessel, and then adding dilute sulfuric acid and copper sulfate pentahydrate into the reaction vessel, wherein the dosage ratio of the paper pulp, the dilute sulfuric acid and the copper sulfate pentahydrate is (10-20) g: (150- & ltSUB & gt-0.4) & gt (preferably 10 g.: 175 mL.: 0.312g) is added, stirring is continued for 2-4h at the water bath temperature of 40-50 ℃, the dispersion is placed in water to stop the reaction after the reaction is finished, then the high-dispersion cellulose nanocrystalline dispersion is obtained by centrifugation, dialyzed to be neutral and concentrated for later use.
Further, the drying in the step (1) is as follows: drying in a vacuum oven at 60 deg.C for 24 h.
Furthermore, the mass percentage concentration of the dilute sulphuric acid is 50-70%.
Further, the preprocessing operation in the step (1) is: the tissue pulp is soaked in sodium hydroxide solution.
Further, the dialysis to neutrality and concentration in the step (2) are: dialyzing the mixture in deionized water by using a dialysis bag to be neutral, and performing rotary evaporation and concentration by using a rotary evaporator to obtain cellulose nanocrystal dispersion, further comprising the following steps: dialyzing to neutrality in deionized water with dialysis bag with molecular weight cutoff of 2000, and rotary evaporating at 60 deg.C with rotary evaporator to obtain 30mg/mL cellulose nanocrystal dispersion.
Further, the mass percent concentration of the sodium hydroxide solution is 3-8%, preferably 4%.
Compared with the prior art, the method has the following advantages:
1. the method takes the cellulose nanocrystals which are wide in source and can be extracted from higher plants in a large scale as the auxiliary stripping reagent, so that the cost for preparing the TMDS nanosheets by aqueous phase ultrasonic stripping is greatly reduced, and compared with other auxiliary stripping reagents, the cellulose nanocrystals have the advantages of being green and environment-friendly.
2. The invention prepares the TMDS nanosheet dispersion liquid (C) with ultrahigh concentration by simply carrying out ultrasonic treatment on the cellulose nanocrystal and TMD in the water phase by virtue of the cavitation action of ultrasonic wavesWS21.81mg/mL), the peeling efficiency reached 18%. Because the cellulose nanocrystalline prepared by the sulfuric acid method with longer reaction time is used as an auxiliary stripping reagent, compared with the cellulose nanofiber, the cellulose nanocrystalline has larger specific surface area and richer surface characteristic groups, and further the cellulose nanocrystalline and the TMDS nanosheet have the advantages ofHas stronger electrostatic attraction and hydrogen bond interaction, which provides a theoretical basis for the peeling and stabilizing process of the cellulose nanocrystal to the TMDS nano-sheets. The technology is adopted to strip TMDS nano sheets, the concentration and the efficiency of the nano sheets are far higher than those of nano sheets prepared by other methods reported at present, and a simple and feasible method is provided for large-scale preparation of the material.
3. The cellulose nanocrystals have excellent water dispersibility, and are used as the stabilizer of the TMDs, so that the stable dispersion of the TMDs nanosheets in the water medium is realized, and the application of the TMDs in the composite material is widened.
4. The high-dispersity cellulose nanocrystalline with a certain length-diameter ratio is prepared through a sulfuric acid acidolysis method, the cellulose nanocrystalline is used as an auxiliary stripping reagent, TMDS powder and the cellulose nanocrystalline are subjected to ultrasonic treatment in an aqueous medium, and the TMDS nanosheet is obtained through successful stripping. Because the cellulose nanocrystalline is a biomass material with wide sources, and the ultrasonic stripping is a simple and feasible stripping method, the TMDS nanosheet prepared by the method is environment-friendly and has low cost. The TMDs nanosheet obtained by final stripping has the characteristic of high concentration, and the method achieves higher nanosheet stripping efficiency, so that good conditions are provided for large-scale preparation of the TMDs nanosheet.
Drawings
FIG. 1A is a schematic diagram of the preparation of cellulose nanocrystals, and FIG. 1B is an atomic force microscope morphology diagram of the cellulose nanocrystals obtained in the example, wherein cellulose nanocrystals with a length of about 176nm and a diameter of about 17nm are prepared from cotton pulp by a sulfuric acid method acidolysis method, and it can be seen that the nanocrystals form stable colloids in water and have good dispersibility.
FIG. 2A shows WS as a final product obtained by peeling in example 1, example 2 and example 3 respectively2、MoS2And WSe2The ultraviolet spectrogram and inset of the dispersion liquid is the corresponding nano-sheet dispersion liquid, which shows that the cellulose nano-crystal is used as an auxiliary stripping reagent to realize the excellent stripping effect of TMDs. Obtaining stably dispersed WS2、 MoS2And WSe2The dispersion liquid respectively shows corresponding characteristic absorption peaks at 638nm, 678nm and 756nm, which shows that the WS is realized2、MoS2And WSe2Successful peeling. The color of the dispersion liquid is yellow green, black green and vermilion, and the concentration of the nano sheet obtained by stripping is relatively high, so that the color is darker. WS obtained in example 1 was analyzed by thermogravimetry2The stripping concentration of the nanosheet reaches 1.81mg/mL (see FIG. 2B), the efficiency is as high as 18%, and the stripping concentration is higher than that obtained by the auxiliary stripping of DNA, sodium alginate and other biomass materials reported at present.
FIG. 3 shows WS obtained by cellulose nanocrystal assisted ultrasonic exfoliation in example 12The size of the obtained nanosheet is about 50-100nm, the appearance is relatively transparent, and the nanosheet is relatively thin.
FIG. 4 shows the MoS obtained by ultrasonic exfoliation assisted by cellulose nanocrystals in example 22The size of the obtained nano sheet is about 100nm-150 nm.
FIG. 5 is the WSe obtained by cellulose nanocrystal assisted ultrasonic exfoliation in example 32The size of the obtained nano sheet is about 100nm-150 nm.
Detailed Description
The invention will be further described with reference to the following figures and examples:
the preparation of concentrated cellulose nanocrystals used in the following examples was as follows:
(1) cotton pulp pretreatment, namely soaking the cotton pulp in a sodium hydroxide solution with the mass fraction of 4% for 24 hours, then performing suction filtration and washing to neutrality, and drying in a vacuum oven at 60 ℃ for 24 hours to obtain the paper pulp;
(2) adding the paper pulp obtained in the step (1) into a reaction container, and then adding 64% by mass of dilute sulfuric acid and blue vitriod into the reaction container, wherein the dosage ratio of the paper pulp, the 64% by mass of dilute sulfuric acid and the blue vitriod is 10 g: 175mL of 0.312g, continuously stirring for 3 hours at the water bath temperature of 45 ℃, and after the reaction is finished, putting the obtained dispersion into 5000mL of water to stop the reaction;
(3) and (3) repeatedly centrifuging the dispersion liquid obtained in the step (2) at 8000rpm for 30min to obtain high-dispersion cellulose nanocrystal dispersion liquid, dialyzing the dispersion liquid to be neutral in deionized water by using a dialysis bag with molecular weight cutoff of 2000, and performing rotary evaporation and concentration at 60 ℃ by using a rotary evaporator to obtain the cellulose nanocrystal dispersion liquid with the concentration of 30mg/mL for later use.
Fig. 1A is a schematic view of preparation of cellulose nanocrystals, and fig. 1B is an atomic force microscope topography of cellulose nanocrystals obtained in example.
Example 1
(1) Diluting the concentrated Cellulose Nanocrystalline (CNC) dispersion liquid to 20mg/mL with deionized water, performing ultrasonic treatment for 5min to realize good dispersion of the cellulose nanocrystalline dispersion liquid, and mixing the diluted dispersion liquid with 150mg WS2Powder (powder size 25-50 μm, WS)2The mass of the powder to volume ratio of CNC dispersion was 10 mg: 1mL) was added to a 25mL glass vial, the two were shaken up and then subjected to ultrasonication at 250W for 30 hours to give a mixed dispersion after exfoliation.
(2) Repeatedly centrifuging the mixed dispersion liquid obtained in the step (1) in a centrifuge at 1500rpm for 30min to remove lower layer large blocks and incompletely peeled WS2Precipitating to obtain supernatant, i.e. final WS2The nano-sheet dispersion is preserved for standby, the color of the dispersion is observed, the stripping can be seen to be thorough, CWS2＝1.81mg/mL。
WS obtained in example 1 was analyzed by thermogravimetry2The exfoliation concentration of the nanoplatelets reached 1.81mg/mL (see FIG. 2B).
FIG. 3 shows WS obtained in this example2The size of the obtained nanosheet is about 50-100nm, the appearance is relatively transparent, and the nanosheet is relatively thin.
Example 2
(1) Diluting the concentrated cellulose nanocrystalline dispersion to 20mg/mL with deionized water, performing ultrasonic treatment for 5min to realize good dispersion of the cellulose nanocrystalline dispersion, and mixing the dispersion with 150mg MoS2Powder (powder size 25-50 μm, MoS)2Mass and CNC of powderThe volume ratio of the powder is 10 mg: 1mL) was added to a 25mL glass vial, the two were shaken up and then subjected to ultrasonication at 250W for 30 hours to give a mixed dispersion after exfoliation.
(2) Repeatedly centrifuging the mixed dispersion liquid obtained in the step (1) in a centrifuge at 1500rpm for 30min to remove lower layer large blocks and incompletely peeled MoS2Precipitating to obtain supernatant, namely the final MoS2And the nanosheet dispersion is stored for later use, and the color of the dispersion is observed, so that the peeling is relatively thorough.
FIG. 4 shows the MoS obtained in this example2The size of the obtained nano sheet is about 100nm-150 nm.
Example 3
(1) Diluting the concentrated cellulose nanocrystal dispersion liquid to 20mg/mL with deionized water, performing ultrasonic treatment for 5min to realize good dispersion of the cellulose nanocrystal dispersion liquid, and mixing the dispersion liquid with 150mg WSe2Powder (powder size 25-50 μm, WSe)2The mass of the powder to volume ratio of CNC dispersion was 10 mg: 1mL) was added to a 25mL glass vial, the two were shaken up and then subjected to ultrasonication at 250W for 30 hours to give a mixed dispersion after exfoliation.
(2) Repeatedly centrifuging the mixed dispersion liquid obtained in the step (1) in a centrifuge at 1500rpm for 30min to remove lower layer large blocks and incompletely peeled WSe2Precipitating to obtain supernatant, namely the final WSe2And the nanosheet dispersion is stored for later use, and the color of the dispersion is observed, so that the peeling is relatively thorough.
FIG. 2A shows WS as a final product obtained by peeling in example 1, example 2 and example 3 respectively2、MoS2And WSe2Ultraviolet spectrum of dispersion.
FIG. 5 shows the WSe obtained in this example2The size of the obtained nano sheet is about 100nm-150 nm.
Example 4
(1) Diluting the concentrated cellulose nanocrystal dispersion with deionized water to 5mg/mL, and ultrasonically treating for 5min to obtain cellulose nanocrystalThe dispersion was well dispersed, and the dispersion was mixed with 150mg WS2Powder (powder size 25-50 μm, WS)2The mass of the powder to volume ratio of CNC dispersion was 10 mg: 1mL) was added to a 25mL glass vial, the two were shaken up and then subjected to ultrasonication at 250W for 30 hours to give a mixed dispersion after exfoliation.
(2) Repeatedly centrifuging the mixed dispersion liquid obtained in the step (1) in a centrifuge at 1500rpm for 30min to remove lower layer large blocks and incompletely peeled WS2Precipitating to obtain supernatant, i.e. final WS2And the nanosheet dispersion is stored for later use, and the color of the dispersion is observed, so that the peeling is relatively thorough.
Example 5
(1) Diluting the concentrated cellulose nanocrystal dispersion liquid to 10mg/mL with deionized water, performing ultrasonic treatment for 5min to realize good dispersion of the cellulose nanocrystal dispersion liquid, and mixing the dispersion liquid with 150mg WS2Powder (powder size 25-50 μm, WS)2The mass of the powder to volume ratio of CNC dispersion was 10 mg: 1mL) was added to a 25mL glass vial, the two were shaken up and then subjected to ultrasonication at 250W for 30 hours to give a mixed dispersion after exfoliation.
(2) Repeatedly centrifuging the mixed dispersion liquid obtained in the step (1) in a centrifuge at 1500rpm for 30min to remove lower layer large blocks and incompletely peeled WS2Precipitating to obtain supernatant, i.e. final WS2And the nanosheet dispersion is stored for later use, and the color of the dispersion is observed, so that the peeling is relatively thorough.
Example 6
(1) Diluting the concentrated cellulose nanocrystal dispersion liquid to 15mg/mL with deionized water, performing ultrasonic treatment for 5min to realize good dispersion of the cellulose nanocrystal dispersion liquid, and mixing the dispersion liquid with 150mg WS2Powder (powder size 25-50 μm, WS)2The mass of the powder to volume ratio of CNC dispersion was 10 mg: 1mL) was added to a 25mL glass vial, and the two were shaken and then sonicated at 250W for 30h to give a mixed dispersion after exfoliation.
(2) The mixed dispersion obtained in the step (1) is put into a centrifuge at 1500rRepeated centrifugation for pm, 30min to remove underlying bulk and incompletely peeled WS2Precipitating to obtain supernatant, i.e. final WS2And the nanosheet dispersion is stored for later use, and the color of the dispersion is observed, so that the peeling is relatively thorough.
Example 7
(1) Subjecting the concentrated 30mg/mL cellulose nanocrystal dispersion to ultrasonic treatment for 5min to realize good dispersion of the cellulose nanocrystal dispersion, and mixing the dispersion with 150mg WS2Powder (powder size 25-50 μm, WS)2The mass of the powder to volume ratio of CNC dispersion was 10 mg: 1mL) was added to a 25mL glass vial, the two were shaken up and then subjected to ultrasonication at 250W for 30 hours to give a mixed dispersion after exfoliation.
(2) Repeatedly centrifuging the mixed dispersion liquid obtained in the step (1) in a centrifuge at 1500rpm for 30min to remove lower layer large blocks and incompletely peeled WS2Precipitating to obtain supernatant, i.e. final WS2And the nanosheet dispersion is stored for later use, and the color of the dispersion is observed, so that the peeling is relatively thorough.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A green, low-cost and efficient preparation method of a transition metal disulfide nanosheet specifically comprises the following steps:
mixing cellulose nanocrystal dispersion liquid with transition metal disulfide nanosheet TMDS powder, and then carrying out ultrasonic treatment and centrifugation to obtain supernatant, namely the final TMDS nanosheet dispersion liquid;
the mass ratio of the cellulose nanocrystals to the TMDS powder in the cellulose nanocrystal dispersion liquid is as follows: (0.5-3): 1.
2. the method according to claim 1, wherein the concentration of the cellulose nanocrystal dispersion is 10 to 50 mg/mL.
3. The method of claim 1, wherein the sonication is: performing ultrasonic treatment for 20-50h under the condition of 250W.
4. The method according to claim 1, wherein the TMDs powder is tungsten disulfide, molybdenum disulfide, or tungsten diselenide powder.
5. The method according to claim 4, wherein the TMDS powder has a size of 25 to 50 μm.
6. The production method according to any one of claims 1 to 5, wherein the cellulose nanocrystal dispersion is produced by:
(1) pretreating the cotton paper pulp by using a sodium hydroxide solution, then carrying out suction filtration, washing to be neutral, and drying to obtain paper pulp;
(2) adding the paper pulp obtained in the step (1) into a reaction vessel, and then adding dilute sulfuric acid and copper sulfate pentahydrate into the reaction vessel, wherein the dosage ratio of the paper pulp, the dilute sulfuric acid and the copper sulfate pentahydrate is (10-20) g: (150-200) mL: (0.2-0.4) g, continuously stirring for 2-4h at the water bath temperature of 40-50 ℃, placing the dispersion into water to stop the reaction after the reaction is finished, then centrifuging to obtain high-dispersion cellulose nanocrystal dispersion, dialyzing to be neutral, and concentrating for later use.
7. The method according to claim 6, wherein the drying in the step (1) is: drying in a vacuum oven at 60 deg.C for 24 h.
8. The method according to claim 6, wherein the dialysis to neutrality and concentration in step (2) are carried out by: dialyzing in deionized water by using a dialysis bag to be neutral, and performing rotary evaporation and concentration by using a rotary evaporator to obtain cellulose nanocrystal dispersion for later use.
9. The method according to claim 6, wherein the sodium hydroxide solution used in the step (1) has a concentration of 3 to 8% by mass.
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