CN106629688A - Temperature-sensitive poly(ionic liquid) water-phase stripping two-dimensional material and application thereof - Google Patents

Temperature-sensitive poly(ionic liquid) water-phase stripping two-dimensional material and application thereof Download PDF

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CN106629688A
CN106629688A CN201611244035.5A CN201611244035A CN106629688A CN 106629688 A CN106629688 A CN 106629688A CN 201611244035 A CN201611244035 A CN 201611244035A CN 106629688 A CN106629688 A CN 106629688A
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boron nitride
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temperature
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王雄伟
武培怡
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Fudan University
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Abstract

The invention belongs to the technical field of two-dimensional laminar materials, in particular to a temperature-sensitive poly(ionic liquid) water-phase stripping two-dimensional material and an application thereof. In particular, three two-dimensional laminar materials, namely, graphite, molybdenum disulfide and boron nitride are stripped by a temperature-sensitive poly(ionic liquid) water phase, and then responsive poly(ionic liquid)-molybdenum disulfide composite hydrogel and high-conductivity stacked boron nitride films are prepared from stripped two-dimensional nanosheets. A preparation method of the material comprises the following steps: firstly, performing common free radical polymerization to obtain temperature-sensitive poly(ionic liquid), and ultrasonically stripping graphite, molybdenum disulfide and boron nitride by a poly(ionic liquid) aqueous solution; secondly, polymerizing ionic liquid in situ by stripped molybdenum disulfide nanosheets to obtain poly(ionic liquid)-molybdenum disulfide composite hydrogel with temperature and near-infrared responses; lastly, performing continuous film pulling by stripped boron nitride nanosheets to obtain high-conductivity boron nitride films. The method is easy to operate, is relatively low in production cost, is easy for batch and large-scale production, and has a wide application prospect.

Description

Temperature sensitive poly ion liquid water mutually peels off two-dimensional material and its application
Technical field
The invention belongs to two-dimensional slice field of material technology, and in particular to a kind of temperature sensitive poly ion liquid water mutually peels off two dimension Sheet layer material and its application.
Background technology
Recently, all kinds of two-dimensional slice materials, such as Graphene, molybdenum bisuphide（MoS2）, tungsten disulfide（WS2）With six sides nitridation Boron（h-BN）, because the properties of their high specific surface areas and uniqueness have attracted extensive concern and research.These materials All there is unique lamella stacked structure, namely one is mutually deposited in along vertical plane direction by Van der Waals force between lamella Rise.Relative to original material, if the two-dimensional material of individual layer or dried layer, because it has great radius-thickness ratio and substantial amounts of exposure Atom is so that also there is significant change, such as heat conductivility, optical property, bandwidth and electrochemistry in its various types of properties Can etc..Chemical vapour deposition technique from bottom to top is considered as the important method for obtaining high quality monolayer two-dimensional nano piece, but Due to its harsh working condition, gentle high vacuum is such as had high demands, and be extremely restricted.Therefore top-to-bottom method is passed through If being considered as most to be hopeful the method that realization is mass produced to peel off the two-dimensional nano piece for obtaining individual layer or dried layer.
Because two-dimensional slice material direction in face has strong chemical bonded, and direction is by weak in vertical plane Van der Waals force connects, therefore is possible by overcoming the Van der Waals force in direction in its vertical plane to carry out stripping to material, and Substantial amounts of experiment also demonstrates this point.At present for the main method of the stripping report of two-dimensional slice material has mechanical stripping, change Learn and peel off, thermal expansion is peeled off etc..Mechanical stripping is due to the features such as comparatively environmentally friendly, simple to operate and suitable large-scale production Receive more concerns.Liquid phase ultrasound is reported from coleman etc. to peel off after all kinds of two-dimensional slice materials, the stripping of liquid phase micromechanics Two-dimensional material is peeled off from research is widely used for.The definition that liquid phase is peeled off is that original two-dimensional material is directly passed through micromechanics If power peels off into the liquid phase the two-dimensional nano piece of individual layer or dried layer.Here micromechanical forces can also be in addition to ultrasonic force cuts Shear force, frictional force etc..Additionally, liquid phase is peeled off usually requires that the solvent for using can preferably soak and disperse the two-dimentional material peeled off Material, namely require that the solvent of selection will be matched with the surface energy of two-dimensional material.But conventional two-dimensional material such as Graphene, nitridation Boron and molybdenum bisuphide etc. carry out liquid phase to it and to peel off often need with high boiling having from some with relatively low surface energy Machine solvent, the such as pyrrolidones of N- methyl -2, DMF, isopropanol.It is envisioned that these higher boilings are organic molten A large amount of uses of agent can bring many problems, and one is that solvent is difficult to remove, and two is not environmentally friendly enough low-carbon (LC), three be operating environment more Badly.Based on these problems that Traditional liquid phase is peeled off, use water as solvent to be considered as to solve to carry out micromechanics to peel off The best approach of these problems.In order to promote hydrophobic two-dimensional material in the dispersion of water phase, it usually needs add some to promote to divide Powder, such as surfactant, some water-soluble polymers, ionic liquid etc..But the effect that the water for promoting dispersant auxiliary is mutually peeled off Rate is typically relatively low, and is generally difficult to universally go to peel off various two-dimensional materials.Therefore how universally to be gone using some way Peel off various two-dimensional materials and be not only water phase micromechanics stripping field, be also a research heat in whole two-dimensional material stripping field Point.
The present invention is just being directed to universally realize that mutually ultrasound peels off graphite, molybdenum bisuphide and nitrogen to water using some way Change boron these three two-dimensional materials.The characteristic of partial ion liquid and the spy of polymer are had concurrently using the temperature sensitive poly ion liquid of synthesis Property, during water mutually peels off two-dimensional material, the positive tetrabutyl phosphonium bromide phosphorus of cationic moiety can be realized inserting two-dimensional material Layer, so as to weaken the interaction force between lamella, and the polystyrolsulfon acid part of anionicsite can be received to stripping Rice piece plays stabilization.Therefore the aqueous solution of the poly ion liquid can simultaneously peel off three kinds of two-dimension nano materials, Er Qieqi PVP and polyvinyl alcohol will be significantly higher than to the peeling effect of molybdenum bisuphide.Additionally due to polyion used Liquid has Thermo-sensitive, therefore can also realize the reversible control of two-dimensional nano piece dispersity of the temperature to peeling off.Further We are using the MoS for peeling off2Nanometer sheet is prepared for good compression recoverability and while there is temperature and near-infrared to ring The MoS of answering property2- PILs hydrogels, have obtained imitative with layer upon layer using BN nanometer sheets are peeled off by way of continuously taking out film The hyperpyrexia guided membrane of mussel structure.
The content of the invention
It is an object of the invention to provide a kind of temperature sensitive poly ion liquid water mutually peel off various two-dimensional materials and its method and Using, i.e., using peel off two-dimensional nano piece preparation temperature, the molybdenum bisuphide-poly ion liquid hydrogel of near-infrared response and The bionical boron nitride of high heat conduction accumulating film layer by layer.
The temperature sensitive poly ion liquid water that the present invention is provided mutually peels off the preparation method of two-dimensional material, concretely comprises the following steps：
（1）Weigh 5-15 g tetrabutyl phosphonium bromides phosphorus and 3-8 g vinyl sodium benzosulfonates are added in 100 ~ 300 ml water, room temperature Lower stirring 2-24, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for, and obtains ionic liquid monomer, is designated as ILs；
（2）Take 1-5 g ILs to be dissolved in 10 ~ 100 ml solvents, add 20 ~ 80 mg azo-bis-isobutyl cyanides, lead to nitrogen 5-60 Reaction 1-12 h in 70 DEG C of oil baths are placed in after min, are re-dissolved in after then reactant liquor is spin-dried in chloroform, be finally stirred vigorously down Precipitation is carried out in n-hexane, poly ion liquid is obtained after drying, be designated as PILs；
（3）Weigh 25 ~ 1000 mg PILs to be dissolved in 20 ~ 200 ml water, be subsequently adding the commercially available molybdenum bisuphide of 0.5 ~ 2 g （MoS2）Powder or boron nitride（BN）Powder or graphite powder, then 6 ~ 32 h of ultrasound in a water bath；After ultrasound terminates, by stripper 10 ~ 40 min are centrifuged under the centrifugal speed of 2000 ~ 8000 rpm, upper liquid is taken, that is, obtain water phase stripping nano piece two dimension material Material（Including：Water mutually peels off molybdenum disulfide nano sheet dispersion liquid, or the boron nitride nanosheet dispersion liquid that water is mutually peeled off）.
Step of the present invention（2）Described in solvent be deionized water, ethanol and N,N-dimethylformamide in one kind.
The present invention prepare water mutually peel off two-dimensional nano piece, can be used for preparation temperature and near-infrared response molybdenum bisuphide- Poly ion liquid（MoS2-PILs）The layer upon layer boron nitride film of composite aquogel and high heat conduction.
Temperature and the MoS of near-infrared response2The preparation process of-PILs composite aquogels is：
Weigh 0.5 ~ 3 g ILs, 40 ~ 150 mg N, N- methylene-bisacrylamides, 10 ~ 60 mg ammonium persulfates and 2 ~ 6 ml The water of 0.1 ~ 0.5 mg/ml is mutually peeled off molybdenum disulfide nano sheet dispersion liquid and is added in 8-10 ml water, leads to nitrogen 10 ~ 30 Min, is then injected into 20 ~ 100 μ L N, and N, N, N- tetramethylethylenediamine stands at room temperature 12 ~ 36 h, obtains MoS2-PILs Composite aquogel.
The preparation process of the layer upon layer boron nitride film of high heat conduction is：
The boron nitride nanosheet dispersion liquid that 20 ~ 50 ml water are mutually peeled off is measured, the polymer of 6 wt% of 0.1 ~ 0.5 ml is added The aqueous solution, after 10 ~ 30 min of ultrasound, is added to take out and continuously taken out in film device film, obtains layer upon layer boron nitride pellicle.
In the present invention, the polymer is the one kind in polyvinyl alcohol, PVP and polyethylene glycol oxide.
The method that the present invention is provided can realize that ultrasound peels off various two-dimensional slice materials in water phase, mainly by closing Into the temperature sensitive poly ion liquid aqueous solution carry out efficiently ultrasound and peel off graphite, molybdenum bisuphide and boron nitride material, then recycle The molybdenum bisuphide of stripping carrys out the molybdenum bisuphide-poly ion liquid hydrogel of preparation temperature and near-infrared response, using the nitrogen peeled off Change boron nanometer sheet Jing and continuously take out the boron nitride high heat conduction film that film obtains layer upon layer.
The composite aquogel that the present invention is prepared using the molybdenum bisuphide peeled off, because poly ion liquid itself is with temperature sensitive Property, and molybdenum bisuphide has a good light thermal property, therefore composite aquogel is sensitive to temperature and near-infrared, with temperature raise by Bottle green becomes white.The boron nitride pellicle of the layer upon layer of preparation, due to piling up tight between boron nitride nanosheet, therefore has There is thermal conductivity in higher face.
The present invention is easy to operate, and preparation condition is simple, low production cost, it is easy to mass, large-scale production, with good The basic and wide application prospect of industrialized production.
Description of the drawings
Fig. 1. dispersity photo of three kinds of two-dimensional slice materials before and after PILs is added in water.
Fig. 2. turbidity change and dispersion in 25 DEG C and 60 DEG C of the 10 wt% PILs aqueous solution in temperature-rise period State photo.
Fig. 3. the dilute dispersion liquid of molybdenum bisuphide, Graphene and boron nitride that peel separation is obtained stands dispersion in front and back in 3 days State photo.
Fig. 4.（a,d）Peel off molybdenum disulfide nano sheet,（b, e）The graphene nanometer sheet of stripping,（c, f）The nitrogen of stripping Change the transmitted electron fibrogram of boron nanometer sheet and the lattice diffraction pattern of response.
Fig. 5.（a）The molybdenum disulfide nano sheet of stripping,（b）The graphene nanometer sheet of stripping,（c）The boron nitride of stripping is received The AFM height map and corresponding altitude curve of rice piece.
Fig. 6.（a）Molybdenum bisuphide before and after stripping,（b）Graphene before and after stripping,（c）The X of the boron nitride before and after stripping X ray diffration pattern x.
Fig. 7.（a）Molybdenum bisuphide before and after stripping,（b）The Raman spectrogram of the Graphene before and after stripping.
Fig. 8.（a）Different PILs concentration of aqueous solution peel off the molybdenum disulfide nano sheet aqueous dispersions that obtain it is ultraviolet-can See spectrogram,（b）PILs peels off what is obtained with PVP and polyvinyl alcohol water solution under the mg/ml of same concentrations 2 Molybdenum bisuphide is received
The UV-visible spectrum of rice piece dispersion liquid.
Fig. 9.（a）Pure PILs hydrogels and MoS2The photo and MoS of-PILS composite aquogels2- PILs composite aquogels The hydrogel color change with near-infrared laser irradiation is raised with temperature.（b）MoS2- PILs composite aquogels are in compression process Change in shape and reply photo.
Figure 10.（a）Pure PILs hydrogels and MoS2The compression stress strain curve of-PILs composite aquogels.（b）MoS2- The Repeated Compression cyclic stress-strain curve of PILs composite aquogels.
Figure 11. (a) continuously take out the photo under normal condition, the rolled state of the boron nitride nanosheet film that film is obtained； （b）The tensile stress strain curve of the boron nitride film of different polyvinyl alcohol contents；（c）Polyvinyl alcohol content is the nitrogen of 7.5 wt% Change the brittle failure Surface scan electron microscope picture of boron film；（d）The thermal conductivity figure of the boron nitride nanosheet film of different polyvinyl alcohol contents.
Specific embodiment
Temperature sensitive poly ion liquid water of the invention is further described by the following examples mutually peels off various two-dimensional slices The preparation method of material and the composite molybdenum disulfide-poly ion liquid hydrogel and layer using the nanometer sheet preparation response peeled off The high heat conduction boron nitride film that layer is piled up, the examples of implementation are merely possible to provide explanation rather than the restriction present invention.
Embodiment 1
（1）Weigh 9.7 g tetrabutyl phosphonium bromides phosphorus and 6 g vinyl sodium benzosulfonates are added in 200 ml water, be stirred at room temperature 24 H, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for obtaining ionic liquid monomer（ILs）；
（2）Take 3 g ILs to be dissolved in 35 ml certain solvent, 48.8 mg azo-bis-isobutyl cyanides are added, after leading to the min of nitrogen 30 Be placed in 70 DEG C of oil baths and react 12 h, be re-dissolved in after then reactant liquor is spin-dried in chloroform, then with vigorous stirring just oneself Precipitation is carried out in alkane, poly ion liquid is obtained after drying（PILs）；
（3）Weigh 200 mg PIL to be dissolved in 100 ml water, be subsequently adding the commercially available molybdenum disulfide powders of 2 g（MoS2）Or 2 g nitrogen Change boron powder（BN）Or 1 g graphite powder, then ultrasonic 18 h in a water bath.After ultrasound terminates, by stripper 3000 rpm's 20 min are centrifuged under centrifugal speed, upper liquid are taken and is the two-dimensional nano piece peeled off；
（4）It is prepared by temperature and near-infrared response composite aquogel：Weigh 2 g ILs, 120 mg N, N- methylene bisacrylamide acyls The MoS that amine, 40 mg ammonium persulfates and the mg/ml of 4 ml 1.25 are above peeled off2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min, are then injected into 60 μ L N, and N, N, N- tetramethylethylenediamine stands at room temperature 36 h, meeting with a response property MoS2- PILs composite aquogels；
（5）It is prepared by the layer upon layer boron nitride film of high heat conduction：The BN nanometer sheet aqueous dispersions that 30 ml are above peeled off are measured, then The aqueous solution of certain polymer of 6 wt% of 0.3 ml is added, after ultrasonic 30 min, is added to take out in film device and is continuously taken out Film, obtains layer upon layer BN film.
The temperature sensitive PILs for synthesizing as seen from Figure 1 has Thermo-sensitive really, and its concentration is the phase transition temperature of the 10 wt% aqueous solution For 56 DEG C or so, solution colour gradually becomes white opacity by clear in phase transition process.Can be seen by Fig. 2, Shao Liangwen The addition of quick PILs can significantly improve dispersion of three kinds of hydrophobic two-dimensional slice materials in water.Can be seen by Fig. 3, PILs The weak solution of three kinds of two-dimensional nano pieces that the aqueous solution is peeled off has excellent dispersion stabilization, appearance is had no after standing 3 days obvious Precipitation, this is because the PILs strands of two-dimensional nano piece adsorption can promote their dispersions in water.Fig. 4 shows The lower ultrasound of Jing PILs auxiliary can be realized being peeled off three kinds of two-dimensional materials really, due to relatively thin, part nanometer of peeling off lamella Piece there occurs curling.In addition can see that the PILs water two-dimensional nano piece that mutually ultrasound stripping is obtained is respectively provided with preferably from diffraction pattern Crystallinity, from terms of lamella edge probably between 4-8 layers.The atomic force microscopy of the two-dimensional material lamella for further being obtained by stripping Height map（Fig. 5）The thickness of molybdenum bisuphide can be seen probably in 2 nm or so, the thickness of graphene sheet layer probably in 2-3 nm, The thickness of boron nitride nanosheet is substantially close with the result of transmission electron microscopy figure probably between 2-4 nm.Before being peeled off by Fig. 6 X-ray diffractogram afterwards can see, molybdenum bisuphide peel off after with respect to initial molybdenum disulfide powder, it is more than 20 degree and spreads out Penetrate peak and be obviously reduced and even disappear；Graphene shows that 26 degree or so of peak is moved to by 26.86 degree before and after peeling off before and after peeling off 26.71 degree, the interlamellar spacing increase between lamella is illustrated, the stacking characteristic peak of the boron nitride before and after stripping is similarly observed that similar Phenomenon.Raman figure before and after being peeled off by Fig. 7 shows, relative to its characteristic peak of initial molybdenum disulfide powder after molybdenum bisuphide stripping E1 2gAnd A1gOccur significantly to move to lower wave number, illustrate the broken of molybdenum disulfide nano sheet and peel off；And for stripping after Graphene its ID/IGValue is significantly increased relative to graphite, and characteristic peak G bands position occurs notable blue shift, and these also all imply graphite The stripping of alkene stripping process lamella is crushed and strong interaction between PILs strands.Conclusions comprehensively can be illustrated PILs can realize mutually peeling off the water of molybdenum bisuphide, boron nitride and graphite really.
Embodiment 2
（1）Weigh 9.7 g tetrabutyl phosphonium bromides phosphorus and 6 g vinyl sodium benzosulfonates are added in 200 ml water, be stirred at room temperature 24 H, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for obtaining ionic liquid monomer（ILs）；
（2）Take 3 g ILs to be dissolved in 35 ml certain solvent, 48.8 mg azo-bis-isobutyl cyanides are added, after leading to the min of nitrogen 30 Be placed in 70 DEG C of oil baths and react 12 h, be re-dissolved in after then reactant liquor is spin-dried in chloroform, then with vigorous stirring just oneself Precipitation is carried out in alkane, poly ion liquid is obtained after drying（PILs）；
（3）Weigh 100 mg PIL to be dissolved in 100 ml water, be subsequently adding the commercially available molybdenum disulfide powders of 2 g（MoS2）Or 2 g nitrogen Change boron powder（BN）Or 1 g graphite powder, then ultrasonic 18 h in a water bath.After ultrasound terminates, by stripper 3000 rpm's 20 min are centrifuged under centrifugal speed, upper liquid are taken and is the two-dimensional nano piece peeled off；
（4）It is prepared by temperature and near-infrared response composite aquogel：Weigh 2 g ILs, 120 mg N, N- methylene bisacrylamide acyls The MoS that amine, 40 mg ammonium persulfates and the mg/ml of 4 ml 1.25 are above peeled off2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min, are then injected into 60 μ L N, and N, N, N- tetramethylethylenediamine stands at room temperature 36 h, meeting with a response property MoS2- PILs composite aquogels；
（5）It is prepared by the layer upon layer boron nitride film of high heat conduction：The BN nanometer sheet aqueous dispersions that 30 ml are above peeled off are measured, then The aqueous solution of certain polymer of 6 wt% of 0.1 ml is added, after ultrasonic 30 min, is added to take out in film device and is continuously taken out Film, obtains layer upon layer BN film.
Embodiment 3
（1）Weigh 9.7 g tetrabutyl phosphonium bromides phosphorus and 6 g vinyl sodium benzosulfonates are added in 200 ml water, be stirred at room temperature 24 H, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for obtaining ionic liquid monomer（ILs）；
（2）Take 3 g ILs to be dissolved in 35 ml certain solvent, 48.8 mg azo-bis-isobutyl cyanides are added, after leading to the min of nitrogen 30 Be placed in 70 DEG C of oil baths and react 12 h, be re-dissolved in after then reactant liquor is spin-dried in chloroform, then with vigorous stirring just oneself Precipitation is carried out in alkane, poly ion liquid is obtained after drying（PILs）；
（3）Weigh 300 mg PIL to be dissolved in 100 ml water, be subsequently adding the commercially available molybdenum disulfide powders of 2 g（MoS2）Or 2 g nitrogen Change boron powder（BN）Or 1 g graphite powder, then ultrasonic 18 h in a water bath.After ultrasound terminates, by stripper 3000 rpm's 20 min are centrifuged under centrifugal speed, upper liquid are taken and is the two-dimensional nano piece peeled off；
（4）It is prepared by temperature and near-infrared response composite aquogel：Weigh 2 g ILs, 120 mg N, N- methylene bisacrylamide acyls The MoS that amine, 40 mg ammonium persulfates and the mg/ml of 4 ml 1.25 are above peeled off2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min, are then injected into 60 μ L N, and N, N, N- tetramethylethylenediamine stands at room temperature 36 h, meeting with a response property MoS2- PILs composite aquogels；
（5）It is prepared by the layer upon layer boron nitride film of high heat conduction：The BN nanometer sheet aqueous dispersions that 30 ml are above peeled off are measured, then The aqueous solution of certain polymer of 6 wt% of 0.2 ml is added, after ultrasonic 30 min, is added to take out in film device and is continuously taken out Film, obtains layer upon layer BN film.
Embodiment 4
（1）Weigh 9.7 g tetrabutyl phosphonium bromides phosphorus and 6 g vinyl sodium benzosulfonates are added in 200 ml water, be stirred at room temperature 24 H, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for obtaining ionic liquid monomer（ILs）；
（2）Take 3 g ILs to be dissolved in 35 ml certain solvent, 48.8 mg azo-bis-isobutyl cyanides are added, after leading to the min of nitrogen 30 Be placed in 70 DEG C of oil baths and react 12 h, be re-dissolved in after then reactant liquor is spin-dried in chloroform, then with vigorous stirring just oneself Precipitation is carried out in alkane, poly ion liquid is obtained after drying（PILs）；
（3）Weigh 400 mg PIL to be dissolved in 100 ml water, be subsequently adding the commercially available molybdenum disulfide powders of 2 g（MoS2）Or 2 g nitrogen Change boron powder（BN）Or 1 g graphite powder, then ultrasonic 18 h in a water bath.After ultrasound terminates, by stripper 3000 rpm's 20 min are centrifuged under centrifugal speed, upper liquid are taken and is the two-dimensional nano piece peeled off；
（4）It is prepared by temperature and near-infrared response composite aquogel：Weigh 2 g ILs, 120 mg N, N- methylene bisacrylamide acyls The MoS that amine, 40 mg ammonium persulfates and the mg/ml of 4 ml 1.25 are above peeled off2Aqueous dispersions are added in 8 ml water, lead to nitrogen 30 min, are then injected into 60 μ L N, and N, N, N- tetramethylethylenediamine stands at room temperature 36 h, meeting with a response property MoS2- PILs composite aquogels；
（5）It is prepared by high heat conduction layer upon layer boron nitride film：Measure the BN nanometer sheet aqueous dispersions that 30 ml are above peeled off, Ran Houjia Enter the aqueous solution of certain polymer of 6 wt% of 0.4 ml, after ultrasonic 30 min, be added to take out in film device and continuously taken out Film, obtains layer upon layer BN film.
Embodiment 5
（1）Weigh 9.7 g tetrabutyl phosphonium bromides phosphorus and 6 g vinyl sodium benzosulfonates are added in 200 ml water, be stirred at room temperature 24 H, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for obtaining ionic liquid monomer（ILs）；
（2）Take 3 g ILs to be dissolved in 35 ml certain solvent, 48.8 mg azo-bis-isobutyl cyanides are added, after leading to the min of nitrogen 30 Be placed in 70 DEG C of oil baths and react 12 h, be re-dissolved in after then reactant liquor is spin-dried in chloroform, then with vigorous stirring just oneself Precipitation is carried out in alkane, poly ion liquid is obtained after drying（PILs）；
（3）Weigh 500 mg PIL to be dissolved in 100 ml water, be subsequently adding the commercially available molybdenum disulfide powders of 2 g（MoS2）Or 2 g nitrogen Change boron powder（BN）Or 1 g graphite powder, then ultrasonic 18 h in a water bath.After ultrasound terminates, by stripper 3000 rpm's 20 min are centrifuged under centrifugal speed, upper liquid are taken and is the two-dimensional nano piece peeled off；
（4）It is prepared by temperature and near-infrared response composite aquogel：Weigh 2 g ILs, 120 mg N, N- methylene bisacrylamide acyls Amine, 40 mg ammonium persulfates are added in 12 ml water, lead to the min of nitrogen 30, are then injected into 60 μ L N, N, N, N- tetramethyl second two Amine, stands at room temperature 36 h, meeting with a response property MoS2- PILs composite aquogels；
（5）It is prepared by high heat conduction layer upon layer boron nitride film：Measure the BN nanometer sheet aqueous dispersions that 30 ml are above peeled off, Ran Houjia Enter the aqueous solution of certain polymer of 6 wt% of 0.5 ml, after ultrasonic 30 min, be added to take out in film device and continuously taken out Film, obtains layer upon layer BN film.
Fig. 8 have studied the aqueous solution of different PILs concentration and the peeling effect of molybdenum bisuphide compared, and use ultraviolet-visible light Compose qualitatively to observe the absorption value of two characteristic peaks, it can be seen that stripping of the PILs aqueous solution of 2 mg/ml to molybdenum bisuphide With best effect.Compared under the mg/ml of same concentration 2 simultaneously, the different water-soluble polymer aqueous solution are to curing The peeling effect of molybdenum, it can be seen that strippings of the PILs relative to PVP and polyvinyl alcohol to molybdenum bisuphide has More preferable effect.
Fig. 9 shows that pure PIls hydrogels are presented clear, and adds the Compound Water of the molybdenum disulfide nano sheet peeled off Gel is presented bottle green.Research MoS2- PILs composite aquogels are found with the rising of temperature to temperature and near infrared response With the irradiation of near-infrared laser, composite aquogel undergoes phase transition, and from original bottle green canescence is changed into.In addition composite aquogel With good compression reaction performance.
Figure 10 tests pure PIls hydrogels and MoS2The compression performance of-PILs composite aquogels, finds composite aquogel Compressive strength to be significantly higher than the hydrogel of pure PIls liquid, and composite aquogel has excellent Repeated Compression cyclicity Energy.
Figure 11 shows that continuously taking out the boron nitride film that film obtains has excellent flexibility and repeatedly bending performance, and studies not Find with the increase of polyvinyl alcohol content with the stress strain curve of the boron nitride film obtained under polyvinyl alcohol addition, boron nitride Tensile strength accordingly increases.Can see that boron nitride film is presented boron nitride nanosheet layer upon layer from the brittle failure face of boron nitride film Imitative mussel structure, is completely embedded between adjacent sheets, and this is conducive to hot being effectively conducted in face.The different polyvinyl alcohol of research contain The thermal conductivity of the lower boron nitride film of amount finds that the thermal conductivity of film reaches maximum when polyvinyl alcohol content is 7.5 wt%, too low and too high Polyvinyl alcohol content be all unfavorable for the raising of thermal conductivity.

Claims (7)

1. temperature sensitive poly ion liquid water mutually peels off the preparation method of two-dimensional material, it is characterised in that concretely comprise the following steps：
（1）Weigh 5-15 g tetrabutyl phosphonium bromides phosphorus and 3-8 g vinyl sodium benzosulfonates are added in 100 ~ 300 ml water, room temperature Lower stirring 2-24, is subsequently adding dichloromethane and is extracted, and takes subnatant and is spin-dried for, and obtains ionic liquid monomer, is designated as ILs；
（2）Take 1-5 g ILs to be dissolved in 10 ~ 100 ml solvents, add 20 ~ 80 mg azo-bis-isobutyl cyanides, lead to nitrogen 5-60 Reaction 1-12 h in 70 DEG C of oil baths are placed in after min, are re-dissolved in after then reactant liquor is spin-dried in chloroform, be finally stirred vigorously down Precipitation is carried out in n-hexane, poly ion liquid is obtained after drying, be designated as PILs；
（3）Weigh 25 ~ 1000 mg PILs to be dissolved in 20 ~ 200 ml water, be subsequently adding the commercially available molybdenum bisuphide of 0.5 ~ 2 g（MoS2） Powder or boron nitride（BN）Powder or graphite powder, then 6 ~ 32 h of ultrasound in a water bath；After ultrasound terminates, by stripper 2000 10 ~ 40 min are centrifuged under the centrifugal speed of ~ 8000 rpm, upper liquid is taken, that is, obtain water phase stripping nano piece two-dimensional material.
2. preparation method according to claim 1, it is characterised in that step（2）Described in solvent be deionized water, second One kind in alcohol and N,N-dimethylformamide.
3. the water phase stripping nano piece two-dimensional material for being prepared by the preparation method described in claim 1.
4. the curing that water phase stripping nano piece two-dimensional material as claimed in claim 1 is responded in preparation temperature and near-infrared Molybdenum-poly ion liquid（MoS2-PILs）Application in the layer upon layer boron nitride pellicle of composite aquogel and high heat conduction.
5. application according to claim 4, it is characterised in that preparation temperature and the molybdenum bisuphide-gather of near-infrared response from Sub- liquid（MoS2-PILs）The preparation process of composite aquogel is：
Weigh 0.5 ~ 3 g ILs, 40 ~ 150 mg N, N- methylene-bisacrylamides, 10 ~ 60 mg ammonium persulfates and 2 ~ 6 ml The water of 0.1 ~ 0.5 mg/ml is mutually peeled off molybdenum disulfide nano sheet dispersion liquid and is added in 8-10 ml water, leads to nitrogen 10 ~ 30 Min, is then injected into 20 ~ 100 μ L N, and N, N, N- tetramethylethylenediamine stands at room temperature 12 ~ 36 h, obtains MoS2-PILs Hydrogel.
6. application according to claim 5, it is characterised in that prepare layer upon layer boron nitride pellicle preparation process be： Measure 20 ~ 50 ml water and mutually peel off boron nitride nanosheet dispersion liquid, add the aqueous solution of the polymer of 6 wt% of 0.1 ~ 0.5 ml, After 10 ~ 30 min of ultrasound, it is added to takes out and continuously taken out in film device film, obtains layer upon layer boron nitride pellicle.
7. application according to claim 6, it is characterised in that the polymer is polyvinyl alcohol, polyvinylpyrrolidone One kind in ketone and polyethylene glycol oxide.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108640154A (en) * 2018-06-15 2018-10-12 西南交通大学 A kind of molybdenum disulfide nano material and preparation method thereof
CN110982011A (en) * 2019-11-29 2020-04-10 河北大学 Light-directing bending material and preparation method thereof
CN112591797A (en) * 2020-12-23 2021-04-02 陕西科技大学 High-concentration high-dispersibility ultrathin molybdenum disulfide dispersion liquid and preparation method thereof
CN112918030A (en) * 2019-12-05 2021-06-08 中国科学院深圳先进技术研究院 Boron nitride film, preparation method thereof, boron nitride composite film containing boron nitride film, thermal interface material and application
CN116574277A (en) * 2023-06-12 2023-08-11 陕西科技大学 Boron nitride/aramid fiber/polyvinyl alcohol heat conduction hydrogel and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111393641B (en) * 2020-03-24 2021-10-12 四川大学 Surfactant capable of simultaneously stripping and vinylating two-dimensional lamellar material, preparation and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1994895A (en) * 2006-12-20 2007-07-11 浙江大学 Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere
CN105161691A (en) * 2015-10-10 2015-12-16 岭南师范学院 Preparation method of less-layer MoS2/phosphorus-doped graphene electrochemical sodium-storage combined electrode
CN105502311A (en) * 2015-12-29 2016-04-20 复旦大学 Preparation method of stripping, functional modification and intelligent composite gel of disulfide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1994895A (en) * 2006-12-20 2007-07-11 浙江大学 Preparation method for ion liquid assisted hydrothermal synthesis of MoS2 microsphere
CN105161691A (en) * 2015-10-10 2015-12-16 岭南师范学院 Preparation method of less-layer MoS2/phosphorus-doped graphene electrochemical sodium-storage combined electrode
CN105502311A (en) * 2015-12-29 2016-04-20 复旦大学 Preparation method of stripping, functional modification and intelligent composite gel of disulfide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YIU-WING MAI 等: "《聚合物纳米复合材料》", 30 April 2010, 机械工业出版社 *
YONGJUN MEN ETC.: "Poly(tetrabutylphosphonium 4-styrenesulfonate): a poly(ionic liquid) stabilizer for graphene being multi-responsive", 《POLYMER CHEMISTRY》 *

Cited By (6)

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CN108640154A (en) * 2018-06-15 2018-10-12 西南交通大学 A kind of molybdenum disulfide nano material and preparation method thereof
CN110982011A (en) * 2019-11-29 2020-04-10 河北大学 Light-directing bending material and preparation method thereof
CN112918030A (en) * 2019-12-05 2021-06-08 中国科学院深圳先进技术研究院 Boron nitride film, preparation method thereof, boron nitride composite film containing boron nitride film, thermal interface material and application
CN112918030B (en) * 2019-12-05 2023-08-08 中国科学院深圳先进技术研究院 Boron nitride film with plane orientation, preparation method thereof, boron nitride composite film containing boron nitride film, thermal interface material and application
CN112591797A (en) * 2020-12-23 2021-04-02 陕西科技大学 High-concentration high-dispersibility ultrathin molybdenum disulfide dispersion liquid and preparation method thereof
CN116574277A (en) * 2023-06-12 2023-08-11 陕西科技大学 Boron nitride/aramid fiber/polyvinyl alcohol heat conduction hydrogel and preparation method thereof

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