CN107381643A - A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material - Google Patents

A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material Download PDF

Info

Publication number
CN107381643A
CN107381643A CN201710713135.6A CN201710713135A CN107381643A CN 107381643 A CN107381643 A CN 107381643A CN 201710713135 A CN201710713135 A CN 201710713135A CN 107381643 A CN107381643 A CN 107381643A
Authority
CN
China
Prior art keywords
van der
der waals
ball
stratified material
stratified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710713135.6A
Other languages
Chinese (zh)
Inventor
段曦东
王剑
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Na Lu Nano Science And Technology Co Ltd
Original Assignee
Guangdong Na Lu Nano Science And Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Na Lu Nano Science And Technology Co Ltd filed Critical Guangdong Na Lu Nano Science And Technology Co Ltd
Publication of CN107381643A publication Critical patent/CN107381643A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0648—After-treatment, e.g. grinding, purification
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/04—Specific amount of layers or specific thickness
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/32—Size or surface area
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • 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
    • C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to field of material technology, specifically discloses the universal method that mechanical stripping Van der Waals stratified material prepares two-dimensional material, including：In the solvent that the stratified material powder of Van der Waals stratified material is dispersed in；The solvent is 1 with Van der Waals stratified material mass ratio:1‑1:5 mixing, and it is 1 to add with Van der Waals quality of materials ratio:10‑1:80 surfactant, then using high energy ball mill, Van der Waals stratified material is peeled off into two-dimensional layer nanometer sheet；In ball milling preparation process, ball milling speed is 200 2500rpm, and Ball-milling Time is 120 360h；After the enough long-times of ball milling, using ethanol wash, then dry, obtain two-dimentional Van der Waals stratified material.The inventive method, can be effectively peeled off Van der Waals stratified material powder, and prepared two-dimensional material has the characteristics of number of plies is few, specific surface area is big.This method equipment is cheap, simple to operate, and production efficiency is high, suitable for mass industrialized production.

Description

A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material
Technical field
The present invention relates to field of material technology, and in particular to a kind of mechanical stripping Van der Waals stratified material prepares two-dimensional material Universal method.
Background technology
In recent years, the two-dimensional material using graphene as representative has started huge great waves in material science, its two-dimensional structure Carry out special performance to material strips.Graphene have high specific strength, excellent photopermeability, electron mobility high and Thermal conductivity factor is high；White graphite alkene equally has high specific strength, photopermeability, thermal conductivity but white graphite alkene tool resistance is high, punctures Voltage is high；Two-dimentional MoS2Possesses good greasy property, research shows the MoS of few layer2Doping is played effectively to steel/steel friction Friction-reducing and antiwear action.The performance of these two-dimensional structures is expected to bring huge change to numerous areas such as photoelectric material, composites Leather, has triggered extensive research of the researcher to two-dimensional material.Using graphene as starting point, people are gradually by two-dimensional material Species is expanded and come, it was found that includes the two-dimensional material of following major class：Class grapheme two-dimension material, the vulcanization of two-dimentional transition metal The layer package material of thing, two dimensional oxidation thing family and other structures, this series of two-dimensional material show exclusive Optimality Energy.
Two-dimensional material possesses excellent performance, has a good application prospect.Preparation of the researcher to two-dimensional material Substantial amounts of energy is put into.The preparation of two-dimensional material can be divided into two kinds of synthesis modes from top to bottom and from bottom to top.From lower and Upper method has the methods of chemical vapor deposition, Hydrothermal Synthesiss, and the equal yield of these methods is extremely low.And two-dimensional material is prepared from top to bottom It is then to be peeled off Van der Waals material by modes such as ultrasound, ball milling, oxidationreductions.Van der Waals stratified material can consider one kind By the two-dimensional material material that stacking gets up on third dimension direction, each atom is combined with chemical bond in its two dimensional surface, but The material that its Van der Waals force passed through between layers on third dimension direction combines.It is to prepare to carry out stripping to Van der Waals material Two-dimensional material is most industrialization method.
The domestic general preparation patent to two-dimensional material is less at present, predominantly ion insertion method, ultrasonic stripping method, chemistry Or physical vaporous deposition and liquid phase method synthesis.But there are many deficiencies in the above method：Oxidation-reduction method use the concentrated sulfuric acid, , certain potential safety hazard be present in the dangerous oxidant such as concentrated nitric acid, potassium permanganate.Reagent majority used in ion insertion method is poisonous, Pollute the environment, and the physical arrangement of ion insertion meeting two-dimensional material and electricity structure produce destruction；Sedimentation yields poorly, into This is high, and efficiency is relatively low as ultrasonic stripping method.
The content of the invention
In view of this, it is necessary in view of the above-mentioned problems, providing a kind of mechanical stripping Van der Waals stratified material prepares two-dimentional material The universal method of material, this method can be effectively peeled off Van der Waals stratified material powder, and prepared two-dimensional material has that the number of plies is few, ratio The characteristics of surface area is big.This method equipment is cheap, simple to operate, and production efficiency is high, suitable for mass industrialized production.
To achieve the above object, the present invention takes following technical scheme：
The mechanical stripping method Van der Waals stratified material of the present invention prepares the universal method of two-dimensional material, including：By Van der Waals Stratified material powder is scattered in a solvent；
The solvent is 5 with Van der Waals stratified material mass ratio:1-1:1 mixing, and surfactant is added, the surface The addition of activating agent is 1 with Van der Waals stratified material mass ratio:10-1:80；Ball mill is used again by Van der Waals stratified material Peel off into two-dimensional layer nanometer sheet；
Can be 200-2500rpm, Ball-milling Time 30- according to different ball mill ball milling speeds in ball milling preparation process 480h；
After the enough long-times of ball milling, using ethanol wash, then dry, obtain two-dimentional Van der Waals stratified material.
As preferable, addition and the Van der Waals stratified material mass ratio of the surfactant are 1:10-1:40.
Further, the ball mill can be planetary ball mill, agitating ball mill, sand mill or other expanding productions Ball mill equipment.
As preferable, the planetary ball mill ball milling speed is 400-600rpm, Ball-milling Time 220-280h；It is described Sand mill ball milling speed is 1500-2500rpm, Ball-milling Time 30-80h；The agitating ball mill ball milling speed is 300- 600rpm, Ball-milling Time 280-400h.
The stratified material that the Van der Waals force combines, during ball milling, the surface energy of solvent for use is close to Van der Waals stratified material Surface energy (Van der Waals stratified material surface energy is about 25-40mJ/m2) when, Van der Waals stratified material charge stripping efficiency highest.
Further, the solvent is low-molecular-weight alcohol and/or ketone and water is 1 in mass ratio:5-2:The mixing of 1 mixing Solution.Wherein alcohol ketone mixes for arbitrary proportion.
Further, the low-molecular-weight alcohol class is one kind in methanol, ethanol, isopropanol, the tert-butyl alcohol or ethylene glycol etc. It is or a variety of；The ketone is at least one of acetone, 2 pentanone or propione.
Further, mechanical milling process is by adding appropriate solvent adjustment material viscosity scope, zirconium ball when buffering ball milling Impact.And when being peeled off due to Van der Waals stratified material ball milling, system viscosity changes greatly, and solvent is must be supplemented with after grinding a period of time With the viscosity of control ball mill body system in the reasonable scope, each addition of solvent is the 5%- of Van der Waals stratified material quality 40%.
Surfactant can fully adsorb on Van der Waals stratified material, to form steric hindrance and electric charge steric hindrance, can promote The two-dimensional nano piece for enter grinding, preventing from having peeled off is reunited.Due to Van der Waals stratified material (stratified material that Van der Waals force combines) Various defects be present, such as：B-B keys in hexagonal AlN be present, this key is easily interrupted；Montmorillonite is due to Al ions in crystal structure A large amount of substitution Si ions, so that surface is negatively charged, are adsorbed with substantial amounts of cation；Deposited in transition metal sulphide crystals structure In substantial amounts of S vacancy defects (such as WS2、MoS2、VS2Deng), and big pi bond be present in this kind of grapheme two-dimension material, can be with there is pi bond Surfactant attract each other.And surfactant used is long-chain lewis base or long-chain lewis acid, can effectively inhale The surface of Van der Waals material is attached to, Electrostatic Absorption is formed with these defects.
Further, the long-chain lewis base includes amount of carbon atom 8-20's：Alkylamine, enamine, mercaptan, carboxylic acid Salt.Such as：Lauryl amine, palmitamide, octadecylamine；Hold amido polyethylene glycol, oleyl amine；Stearic acid, palmitic acid, palmitic acid, oil Acid, linoleic acid；Lauryl mercaptan, 1- certain herbaceous plants with big flowers mercaptan, hexadecanethiol, 1- nonyls mercaptan, the mercaptan of uncle 16,1- undecane thiols, positive ten Five alkyl hydrosulfides, tert- tetradecanes mercaptan, polyphenylacetylene, polythiophene, kayexalate, detergent alkylate, 4- dodecanes Base aniline, polyoxyethylene octane alkylphenol ether, glycidol 12-14 alkyl ethers, six polyethyleneglycol margarons etc..
The long-chain lewis acid includes：Amount of carbon atom is 8-20's in molecule：Alkylammonium salt, carboxylic acid etc..Such as：12 Alkyl trimethyl ammonium salt, cetyltrimethyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, dodecyl dimethyl hexadecyldimethyl benzyl ammonium Salt；Stearate, palmitate, oleate etc..
Compared with prior art, beneficial effects of the present invention are：
Two-dimensional nano piece sheet thickness prepared by the present invention is respectively less than 10nm, in addition can as little as several nanometers, grain size Hundreds of nanometers to a few micrometers are distributed in, specific surface area is up to 100-200m2/g。
Without soda acid, without toxic organic additive etc. in preparation process of the present invention, green, production efficiency is high, production Amount is big, and equipment is cheap.Prepared two-dimentional Van der Waals stratified material particle diameter is big, thickness of thin, specific surface area are big, has good Application prospect.
Brief description of the drawings
Fig. 1 is the SEM photograph of the Van der Waals stratified material prepared by embodiment 1.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair Bright technical scheme is made further clearly and completely to describe.It should be noted that described embodiment is only the present invention one Section Example, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not doing Go out under the premise of creative work the every other embodiment obtained, belong to the scope of protection of the invention.
Van der Waals stratified material has layer structure, in some crystalline axis direction, forms the atoms perpendicular of the crystal crystallographic axis shape Into atomic layer, atom is arranged parallel to each other with the strong chemical bonds such as covalent bond, atom interlayer in layer, with weak Van der Waals force It is combined, Van der Waals stratified material includes but is not limited to：Graphite；Hexagonal boron nitride；Black phosphorus；The transition metal such as molybdenum disulfide two Chalcogenide (the MoS of semiconductive2、WS2、WSe2、NbSe2、ZrS2、ZrSe2, the NbS of metallicity2、TiS2、TaS2、 NiSe2、NbSe2)；Chalcogenide (the NbX of transition metal three3、TiX3、TaX3, X=S, Se, Te；The chalcogenide of metal phosphorus three, Such as MnPS3、CdPS3、NiPS3、ZnPS3Deng)；Metal halide (PbI2、BiI3、MoCl2、PbCl4)；Layered oxide (Bi2Sr2CaCu2OxSr2Nb3O10、TiO2、Ti3O7、MnO2、MoO3、WO3、V2O5, the LaNbO of perovskite structure7、Bi4Ti3O12 Deng)；Transition metal oxyhalide (VOCl, CdOCl, FeOCl, NbO2F、WO2Cl2Deng)；Layered hydroxide (Ni (OH)2、Eu (OH)2Deng)；Phyllosilicate ([(Mg3)(Si2O5)2(OH)2]、[(Al2)(Si3Al)O10(OH)2]K、[(Al2)(Si2Al2)O10 (OH)2]Ca；[(Mg6)(Si6Al2)O20(OH)4]、[(MgFe)3(Si3Al)O10(OH)2]K、[Mg11/4(Si6Al2)O20F4]- [(M2+)3/2])；Metal carbides and nitride (MAX, M=transition metal；A=Al, Si；X=C or N, WC2)；Other stratiforms half Conductor (GaSe, GaTe, InSe, GeS, In2Se3、Bi2Se3Deng)；Etc..
Embodiment 1
The specific preparation technology of the implementation case comprises the following steps：By 100g MoS2It is scattered in 100g ethanol and 100g water In the solvent of configuration, 4g ends amido polyethylene glycol is weighed, stirring is allowed to be completely dispersed, and is transferred in ball grinder.
It is fixed on after ball grinder sealing on planetary ball mill, starts ball mill, with 550rpm ball millings 140h.Ball milling first My god, often cross 6h addition 25ml ethanol water (ethanol：Water quality ratio is 1:1)；Ball milling the 2nd day to the 4th day, added per 24h 25ml ethanol waters.After Ball-milling Time was more than 5 days, 10ml ethanol waters are added daily.
By MoS after ball milling2Slurry filters after ethanol wash, by gained filtering layer in Muffle furnace at 80 DEG C of drying Reason obtains MoS2Nanometer sheet.
Fig. 1 is the SEM photograph of the present embodiment sample, it can be seen that being peeled off by ball milling, resulting MoS2Nanometer Piece particle diameter is up to a few micrometers, two-dimentional MoS2Thickness can as little as several nanometers, is characterized by BET and finds that its specific surface area is 158m2/g。
Embodiment 2
The specific preparation technology of the present embodiment comprises the following steps：Weigh 1000g deionized waters, 1000g ethanol stirs in container Mix and be configured to uniform solution.Weigh 800g white graphite alkene to be scattered in above-mentioned alcohol water blend, add 37.5g oleyl amines, stirring It is allowed to be completely dispersed.
The good slurry of above-mentioned configuration is added in 3L sand mill barrels, opens sand mill with 2000rpm start ball millings, ball During mill 100ml ethanol water (ethanol is supplemented every 6h：Water quality ratio is 1：1) to adjust viscosity, after ball milling 36h, receive Material.
Slurry is filtered after ethanol wash, and filtering layer is obtained into montmorillonite-based nano piece, gained montmorillonite-based nano in 80 DEG C of drying Piece characterizes by BET, and its specific surface area is 363m2/g。
Embodiment 3
The specific preparation technology of the present embodiment comprises the following steps：Weigh 1000g deionized waters, 1000g ethanol stirs in container Mix and be configured to uniform solution.Weigh 800g montmorillonites to be scattered in above-mentioned alcohol water blend, add 40g octadecyldimethyls Benzyl ammonium chloride, stirring are allowed to be completely dispersed.
The good slurry of above-mentioned configuration is added in 5L agitating ball mill barrels, opens sand mill with 400rpm start balls Grind, 24h often crosses 6h addition 100ml ethanol water (ethanol before ball milling：Water quality ratio is 1:1)；Ball milling the 2nd day to the 4th day, often 100ml ethanol waters are supplemented every 24h, Ball-milling Time per 24h more than 50g alcohol water blends are added after 72h, to adjust viscosity, Rewinding after ball milling 280h.
Slurry is filtered after ethanol wash, 80 DEG C of drying obtain montmorillonite-based nano piece, and gained montmorillonite-based nano piece passes through BET is characterized, and its specific surface area is 242m2/g。
Embodiment 4
The specific preparation technology of the implementation case comprises the following steps：By 100g graphite dispersions in 100g ethanol and 100g go from In the solvent of sub- water configuration, 10g polythiophenes are measured, stirring is allowed to be completely dispersed, and is transferred in ball grinder.
Ball grinder is sealed, is fixed on ball mill, starts ball mill, with 450rpm ball millings 240h.Ball milling first day, Often cross 6h addition 25ml ethanol water (ethanol：Water quality ratio is 1:1)；Ball milling the 2nd day to the 4th day, the addition 25ml second per 24h Alcohol solution.After Ball-milling Time was more than 5 days, 1 day addition 10ml ethanol water is often crossed.
Graphene slurry is filtered after ball milling, after ethanol wash, 80 DEG C of drying and processings obtain in Muffle furnace Graphene nanometer sheet, characterize and find that its specific surface area is 498m2/g。
Embodiment 5
The specific step of preparation process of the implementation case：By 5000g white graphite alkene be scattered in 5000g ethanol and 5000g go from In the solvent of sub- water configuration, 200g polythiophenes are measured, stirring is allowed to be completely dispersed, and is transferred in ball grinder.
Transfer the material into ball mill barrel, start ball mill, with 400rpm ball millings 280h.Preceding 24h in mechanical milling process The addition 200g aqueous acetone solutions per 2h.Ball-milling Time reaches 24-72h, the addition 100g aqueous acetone solutions per 24h.Ball-milling Time exceedes 50g aqueous acetone solutions are added after 72h per 24h, to ensure that ball milling system possesses suitable viscosity.
Ball milling is finished by white graphite alkene after ethanol wash, and 80 DEG C of drying and processings obtain ball milling white graphite in Muffle furnace Alkene product.
White graphite alkene nanometer sheet particle diameter obtained by the present embodiment is more than 250nm, and nanometer sheet thickness is below 10nm；Big portion The thickness for dividing h-BN pieces is 4nm, and part h-BN thickness can as little as 1nm or so.It is 220m by detecting specific surface area2/g。
Embodiment 6
The specific preparation technology of the implementation case comprises the following steps：Weigh 200gWS2, 100g acetone and 100g deionized waters In ball grinder, stirred with glass bar.Measure 4g polyethylene glycol diamines, be put into ball grinder, same stirring makes its complete Dissolving.
Ball grinder is sealed, is fixed on planetary ball mill, starts ball mill, with 450rpm ball millings 240h.Ball milling One day, often cross 6h addition 25ml ethanol water (ethanol：Water quality ratio is 1:1)；Ball milling the 2nd day to the 4th day, added per 24h 25ml ethanol waters.After Ball-milling Time was more than 5 days, 1 day addition 10ml ethanol water is often crossed.
By WS after ball milling 240h2Slurry filters, and with ethanol wash, 80 DEG C are dried to obtain WS in Muffle furnace2Nanometer sheet, table Its existing specific surface area of levying is 318m2/g。
Embodiment 7
The specific preparation technology of the implementation case comprises the following steps：Weigh 200gWS2, 50g acetone and 150g deionized waters, 4g stearic acid is measured, is put into ball grinder, stirring is completely dissolved it.
It is fixed on after ball grinder sealing on planetary ball mill, starts ball mill, with 500rpm ball millings 240h.Ball milling first My god, often cross 6h addition 25ml ethanol water (ethanol：Water quality ratio is 1:1)；Ball milling the 2nd day to the 4th day, added per 24h 25ml ethanol waters.After Ball-milling Time was more than 5 days, 1 day addition 10ml ethanol water is often crossed.
By WS after ball milling 240h2Slurry filters, and after ethanol wash, 80 DEG C are dried to obtain ball milling WS in Muffle furnace2Nanometer Piece, characterize and find that its specific surface area is 358m2/g。
Embodiment 8
The specific preparation technology of the implementation case comprises the following steps：Weigh 200gVS2, 100g acetone and 100g deionizations Water, 4g oleyl amines are measured, are put into ball grinder, stirring is allowed to be completely dissolved.
It is fixed on after ball grinder sealing on planetary ball mill, starts ball mill, with 500rpm ball millings 240h.Ball milling first My god, often cross 6h addition 25ml ethanol water (ethanol：Water quality ratio is 1:1)；Ball milling the 2nd day to the 4th day, added per 24h 25ml ethanol waters.After Ball-milling Time was more than 5 days, 1 day addition 10ml ethanol water is often crossed.
By VS after ball milling 240h2Slurry filters, and after ethanol wash, 80 DEG C are dried to obtain VS in Muffle furnace2Nanometer sheet, Characterize and find that its specific surface area is 336m2/g。
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (9)

1. a kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material, it is characterised in that including：By model moral The stratified material powder of magnificent stratified material is scattered in a solvent；
The solvent is 5 with Van der Waals stratified material mass ratio:1-1:1 mixing, and surfactant is added, the surface-active The addition of agent surfactant is 1 with Van der Waals stratified material mass ratio:10-1:80；Ball mill is used again, by Van der Waals layer Shape material is peeled off into two-dimensional layer nanometer sheet；
In ball milling preparation process, ball milling speed 200-2500rpm, Ball-milling Time 30-480h；
After the enough long-times of ball milling, using ethanol wash, then dry, obtain two-dimentional Van der Waals stratified material.
2. mechanical stripping Van der Waals stratified material according to claim 1 prepares the universal method of two-dimensional material, its feature It is, during ball milling, the surface energy of the surface energy of solvent for use close to Van der Waals stratified material.
3. mechanical stripping Van der Waals stratified material according to claim 1 prepares the universal method of two-dimensional material, its feature It is, the solvent is low-molecular-weight alcohol and/or ketone and water is 1 in mass ratio:5-2:The mixed solution of 1 mixing.
4. mechanical stripping Van der Waals stratified material according to claim 3 prepares the universal method of two-dimensional material, its feature It is, the low-molecular-weight alcohol class is the one or more in methanol, ethanol, isopropanol, the tert-butyl alcohol or ethylene glycol；The ketone For at least one of acetone, 2 pentanone or propione.
5. mechanical stripping Van der Waals stratified material according to claim 1 prepares the universal method of two-dimensional material, its feature It is, the surfactant is long-chain lewis base or long-chain lewis acid.
6. mechanical stripping Van der Waals stratified material according to claim 1 prepares the universal method of two-dimensional material, its feature It is,
The long-chain lewis base includes amount of carbon atom 8-20's：Alkylamine, enamine, mercaptan, carboxylate；
The long-chain lewis acid includes：Amount of carbon atom is 8-20's in molecule：Alkylammonium salt, carboxylic acid.
7. the mechanical stripping Van der Waals stratified material according to claim 1-6 any one prepares the general side of two-dimensional material Method, it is characterised in that mill a period of time after supplementing solvent with the viscosity of control ball mill body system in the reasonable scope, solvent adds every time Enter the 5%-40% that amount is Van der Waals stratified material quality.
8. mechanical stripping Van der Waals stratified material according to claim 1 prepares the universal method of two-dimensional material, its feature It is, described ball mill includes planetary ball mill, sand mill, agitating ball mill.
9. mechanical stripping Van der Waals stratified material according to claim 8 prepares the universal method of two-dimensional material, its feature It is, the planetary ball mill ball milling speed is 400-600rpm, Ball-milling Time 220-280h；The sand mill ball milling speed For 1500-2500rpm, Ball-milling Time 30-80h；The agitating ball mill ball milling speed is 300-600rpm, and Ball-milling Time is 280-400h。
CN201710713135.6A 2016-12-12 2017-08-18 A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material Pending CN107381643A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2016111407453 2016-12-12
CN201611140745.3A CN106744875A (en) 2016-12-12 2016-12-12 A kind of method that ball milling peels off white graphite alkene

Publications (1)

Publication Number Publication Date
CN107381643A true CN107381643A (en) 2017-11-24

Family

ID=58880237

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201611140745.3A Pending CN106744875A (en) 2016-12-12 2016-12-12 A kind of method that ball milling peels off white graphite alkene
CN201710713135.6A Pending CN107381643A (en) 2016-12-12 2017-08-18 A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material
CN201710714410.6A Pending CN107352516A (en) 2016-12-12 2017-08-18 A kind of method that ball milling peels off white graphite alkene

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201611140745.3A Pending CN106744875A (en) 2016-12-12 2016-12-12 A kind of method that ball milling peels off white graphite alkene

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201710714410.6A Pending CN107352516A (en) 2016-12-12 2017-08-18 A kind of method that ball milling peels off white graphite alkene

Country Status (2)

Country Link
CN (3) CN106744875A (en)
WO (1) WO2018107795A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108163894A (en) * 2017-12-21 2018-06-15 浙江山峪科技股份有限公司 A kind of ultrahigh concentration stripping means of transient metal sulfide
CN108455541A (en) * 2018-03-22 2018-08-28 刘丹 The preparation method and functionalized nano film of functionalization two-dimension nano materials
CN108946817A (en) * 2018-08-10 2018-12-07 陕西科技大学 It is a kind of that δ-MnO is removed by liquid nitrogen frozen2The method for obtaining nanometer sheet
CN109941992A (en) * 2019-04-09 2019-06-28 广东墨睿科技有限公司 A kind of Mechanical Method removing graphene of coating and preparation method thereof
WO2020027041A1 (en) * 2018-07-30 2020-02-06 株式会社Adeka Method for producing composite material
CN111203255A (en) * 2020-01-16 2020-05-29 西安交通大学 N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst
CN111933918A (en) * 2020-06-28 2020-11-13 武汉理工大学 Preparation method of two-dimensional metal bismuth and application of two-dimensional metal bismuth in sodium/potassium ion secondary battery
CN115287625A (en) * 2022-07-08 2022-11-04 武汉大学 Method for preparing two-dimensional non-layered narrow-band-gap semiconductor material based on Van der Waals epitaxy
WO2024026785A1 (en) * 2022-08-04 2024-02-08 苏州大学 Two-dimensional nanosheet and preparation method therefor

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106744875A (en) * 2016-12-12 2017-05-31 广东纳路纳米科技有限公司 A kind of method that ball milling peels off white graphite alkene
CN109749374A (en) * 2019-01-08 2019-05-14 常州兴烯石墨烯科技有限公司 Modified white graphite alkene terylene compound slice of a kind of in-situ polymerization and preparation method thereof
CN111115591A (en) * 2020-01-03 2020-05-08 青岛科技大学 Ultra-high concentration boron nitride nano paste and preparation method thereof
CN111568806B (en) * 2020-04-14 2023-03-10 仲恺农业工程学院 Essential oil-loaded biological polysaccharide and protein modified boron nitride and preparation method and application thereof
US20220157477A1 (en) * 2020-11-13 2022-05-19 HB11 Energy Holdings Pty Limited Materials for nuclear fusion
CN112456455A (en) * 2020-12-15 2021-03-09 中国科学院兰州化学物理研究所 Method for preparing boron nitride nanoparticles by ball milling method
CN112919431B (en) * 2021-02-07 2023-07-18 辽东学院 Hexagonal boron nitride nano-sheet with high yield and high crystallinity and preparation method thereof
CN114410276B (en) * 2021-12-13 2023-06-13 长安大学 Preparation method of ball milling process control agent
CN116920024A (en) * 2023-01-31 2023-10-24 百草边大生物科技(青岛)有限公司 Large biological functional agent containing soapberry extract

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104495826A (en) * 2014-12-25 2015-04-08 北京航空航天大学 Single-layer graphene dispersion liquid and preparation method thereof
CN104671235A (en) * 2013-11-28 2015-06-03 中国科学院理化技术研究所 Dispersion solution of graphene nanosheet and preparation method of dispersion solution
CN104959050A (en) * 2015-04-29 2015-10-07 北京天恒盛通科技发展有限公司 Highly dispersed highly stable high concentration and high yield graphene dispersion liquid and preparation method thereof
CN105271185A (en) * 2014-06-25 2016-01-27 中国科学院苏州纳米技术与纳米仿生研究所 Two-dimensional lamellar structure stable dispersion liquid and gel, and preparation method and application thereof
CN105752977A (en) * 2016-04-29 2016-07-13 江苏超电新能源科技发展有限公司 Preparation method of high-conductivity graphene powder
CN105800594A (en) * 2016-02-19 2016-07-27 四川大学 Graphene material based on solid state mechanochemical reactor and preparation method of graphene material

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8303922B2 (en) * 2009-08-24 2012-11-06 The United States Of America As Represeted By The Administrator Of The National Aeronautics And Space Administration Method for exfoliation of hexagonal boron nitride
CN101817516A (en) * 2010-05-21 2010-09-01 哈尔滨工业大学 Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping
CN103570003B (en) * 2012-07-25 2016-03-16 中国科学院大连化学物理研究所 A kind of method of macroscopic preparation of graphene and two-dimentional boron nitride crystal material
GB201304770D0 (en) * 2013-03-15 2013-05-01 Provost Fellows Foundation Scholars And The Other Members Of Board Of A scalable process for producing exfoliated defect-free, non-oxidised 2-dimens ional materials in large quantities
CN103407990B (en) * 2013-07-08 2016-08-31 清华大学深圳研究生院 A kind of grapheme material and preparation method thereof
CN103466608B (en) * 2013-09-11 2015-09-02 中南大学 A kind of ball milling preparation method of Graphene
CN105883754A (en) * 2014-12-09 2016-08-24 戴加龙 High-efficiency production method of graphene
CN106744875A (en) * 2016-12-12 2017-05-31 广东纳路纳米科技有限公司 A kind of method that ball milling peels off white graphite alkene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104671235A (en) * 2013-11-28 2015-06-03 中国科学院理化技术研究所 Dispersion solution of graphene nanosheet and preparation method of dispersion solution
CN105271185A (en) * 2014-06-25 2016-01-27 中国科学院苏州纳米技术与纳米仿生研究所 Two-dimensional lamellar structure stable dispersion liquid and gel, and preparation method and application thereof
CN104495826A (en) * 2014-12-25 2015-04-08 北京航空航天大学 Single-layer graphene dispersion liquid and preparation method thereof
CN104959050A (en) * 2015-04-29 2015-10-07 北京天恒盛通科技发展有限公司 Highly dispersed highly stable high concentration and high yield graphene dispersion liquid and preparation method thereof
CN105800594A (en) * 2016-02-19 2016-07-27 四川大学 Graphene material based on solid state mechanochemical reactor and preparation method of graphene material
CN105752977A (en) * 2016-04-29 2016-07-13 江苏超电新能源科技发展有限公司 Preparation method of high-conductivity graphene powder

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108163894A (en) * 2017-12-21 2018-06-15 浙江山峪科技股份有限公司 A kind of ultrahigh concentration stripping means of transient metal sulfide
CN108455541A (en) * 2018-03-22 2018-08-28 刘丹 The preparation method and functionalized nano film of functionalization two-dimension nano materials
JPWO2020027041A1 (en) * 2018-07-30 2021-08-02 株式会社Adeka Method of manufacturing composite materials
WO2020027041A1 (en) * 2018-07-30 2020-02-06 株式会社Adeka Method for producing composite material
JP7407711B2 (en) 2018-07-30 2024-01-04 株式会社Adeka Composite material manufacturing method
TWI821345B (en) * 2018-07-30 2023-11-11 日商艾迪科股份有限公司 Manufacturing methods of composite materials
CN112424293A (en) * 2018-07-30 2021-02-26 株式会社艾迪科 Method for producing composite material
CN108946817A (en) * 2018-08-10 2018-12-07 陕西科技大学 It is a kind of that δ-MnO is removed by liquid nitrogen frozen2The method for obtaining nanometer sheet
CN109941992A (en) * 2019-04-09 2019-06-28 广东墨睿科技有限公司 A kind of Mechanical Method removing graphene of coating and preparation method thereof
CN111203255B (en) * 2020-01-16 2021-05-28 西安交通大学 N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst
CN111203255A (en) * 2020-01-16 2020-05-29 西安交通大学 N-doped CdPS3Preparation method of two-dimensional nanosheet photocatalyst
CN111933918B (en) * 2020-06-28 2022-03-04 武汉理工大学 Preparation method of two-dimensional metal bismuth and application of two-dimensional metal bismuth in sodium/potassium ion secondary battery
CN111933918A (en) * 2020-06-28 2020-11-13 武汉理工大学 Preparation method of two-dimensional metal bismuth and application of two-dimensional metal bismuth in sodium/potassium ion secondary battery
CN115287625A (en) * 2022-07-08 2022-11-04 武汉大学 Method for preparing two-dimensional non-layered narrow-band-gap semiconductor material based on Van der Waals epitaxy
WO2024026785A1 (en) * 2022-08-04 2024-02-08 苏州大学 Two-dimensional nanosheet and preparation method therefor

Also Published As

Publication number Publication date
CN106744875A (en) 2017-05-31
WO2018107795A1 (en) 2018-06-21
CN107352516A (en) 2017-11-17

Similar Documents

Publication Publication Date Title
CN107381643A (en) A kind of mechanical stripping Van der Waals stratified material prepares the universal method of two-dimensional material
Zhao et al. Metastable MoS2: crystal structure, electronic band structure, synthetic approach and intriguing physical properties
Zhuang et al. Three-dimensional molybdenum disulfide/graphene hydrogel with tunable heterointerfaces for high selective Hg (II) scavenging
Yin et al. Ultrathin two-dimensional layered metal hydroxides: an emerging platform for advanced catalysis, energy conversion and storage
He et al. Controlled synthesis of Co3O4 nanoparticles through oriented aggregation
Dong et al. A facile one-step solvothermal synthesis of graphene/rod-shaped TiO 2 nanocomposite and its improved photocatalytic activity
Yan et al. Formation of ultrafine three-dimensional hierarchical birnessite-type MnO2 nanoflowers for supercapacitor
Gunjakar et al. Exploration of nanostructured functional materials based on hybridization of inorganic 2D nanosheets
Rauda et al. General method for the synthesis of hierarchical nanocrystal-based mesoporous materials
Ma et al. α-Fe2O3: hydrothermal synthesis, magnetic and electrochemical properties
Lv et al. Highly efficient removal of As (V) by using NiAl layered double oxide composites
Hussain et al. Recent advances in oriented metal–organic frameworks for supercapacitive energy storage
Li et al. Synthesis and characterization of hollow MoS2 microspheres grown from MoO3 precursors
Liang et al. Self-assembled 3D flower-like α-Fe2O3 microstructures and their superior capability for heavy metal ion removal
Song et al. Bottom-up approach design, band structure, and lithium storage properties of atomically thin γ-FeOOH nanosheets
Qu et al. Preparation and interfacial properties of ultralow concentrations of amphiphilic molybdenum disulfide nanosheets
Tolstoy et al. Synthesis of birnessite structure layers at the solution–air interface and the formation of microtubules from them
Scott et al. Synthesis of metal sulfide materials with controlled architecture
Zhang et al. Interface-induced enhanced electromagnetic wave absorption property of metal-organic frameworks wrapped by graphene sheets
Gao et al. Synthesis and characterization of organic–inorganic hybrid GeOx/ethylenediamine nanowires
Chen et al. Easily removable visible-light-driven photocatalyst of nickel modified SnS2 nanosheets for reduction of Cr (VI)
Zang et al. Synthesis and magnetic properties of new [Fe18S25](TETAH) 14 (TETAH= protonated triethylenetetramine) nanoribbons: An efficient precursor to Fe7S8 nanowires and porous Fe2O3 nanorods
Zhang et al. Large-scale preparation, chemical exfoliation, and structural modification of layered zinc hydroxide nanocones: transformation into zinc oxide nanocones for enhanced photocatalytic properties
Jassem et al. The effect of temperature on structural and optical properties of manganese oxide nanoparticles
Ding et al. Efficient exfoliation of layered materials by waste liquor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20171124

RJ01 Rejection of invention patent application after publication