CN109250718A - A kind of removing Ti3C2The method of nanometer sheet - Google Patents
A kind of removing Ti3C2The method of nanometer sheet Download PDFInfo
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- CN109250718A CN109250718A CN201710571358.3A CN201710571358A CN109250718A CN 109250718 A CN109250718 A CN 109250718A CN 201710571358 A CN201710571358 A CN 201710571358A CN 109250718 A CN109250718 A CN 109250718A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of removing Ti3C2The method of nanometer sheet, comprising: S1) by Ti3MC2It is mixed with hydrofluoric acid, the powder after being stirred to react, after being etched；The M is Al, Si or Ge；S2) powder after the etching is heated, is then contacted with cryogenic liquid, intermediate is obtained；S3 the intermediate is ultrasonically treated in water), obtains Ti3C2Nanometer sheet.Compared with prior art, the present invention uses cryogenic liquid for medium, and using it, fast vaporizing green removes two dimension Ti at high temperature3C2Nanometer sheet, stripping means implementing process is simple, process is controllable, it is worth with stronger promotion and application, and without using toxicity organic reagents such as dimethyl sulfoxide or dimethylformamides, green removing is realized, sonication treatment time also greatly shortens, and low energy consumption, belong to environmentally friendly chemical preparation process, meets the preparation trend of current low energy consumption.
Description
Technical field
The invention belongs to two-dimensional material technical field more particularly to a kind of removing Ti3C2The method of nanometer sheet.
Background technique
After the discovery of graphene, two-dimensional material has become a Main way in material science research.As two-dimentional material
Expect a member new in family, transition metal carbide MXenes has been received more and more attention, wherein " M " indicates transition gold
Belong to, " X " indicates nitride or carbide.Studying in current MXenes material most is exactly adequately Ti3C2。Ti3C2It is usually to pass through
Removing is by the Ti of hf etching3AlC2It obtains.
After the discovery of MXenes material, constantly reported with many excellent properties, such as: the heat of MXenes passes
It leads performance and multi-layer graphene is similar, Density function theory display MXenes is very rigid, and (elastic constant is more than in face
500GPa), and with flexibility, excellent structural stability, high conductance and hydrophily.These excellent properties make Ti3C2?
It is widely used in the fields such as supercapacitor, lithium ion battery, lubriation material and heavy metal adsorption.
Removing Ti at present3C2The method that two-dimensional nano piece is widely used is ultrasonic liquid-phase removing, i.e., is carved first by hydrofluoric acid
Eating away Ti3AlC2In Al atom, then remove to obtain the Ti containing functional group by long-time ultrasonic disperse in organic solvent3C2
Two-dimensional nano piece.But the toxic organic solvents such as dimethyl alum or dimethylformamide will be used in ultrasonic disperse removing, this
It is runed counter to current advocated Green Chemistry, and the large power supersonic time is also up to 20h or so, this undoubtedly greatly increases energy consumption.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of environmentally friendly and lower removing Ti of energy consumption3C2It receives
The method of rice piece.
The present invention provides a kind of removing Ti3C2The method of nanometer sheet, comprising:
S1) by Ti3MC2It is mixed with hydrofluoric acid, the powder after being stirred to react, after being etched；The M is Al, Si or Ge；
S2) powder after the etching is heated, is then contacted with cryogenic liquid, intermediate is obtained；
S3 the intermediate is ultrasonically treated in water), obtains Ti3C2Nanometer sheet.
Preferably, the Ti3MC2Size be 500~20000nm.
Preferably, the mass concentration of the hydrofluoric acid is 30%~60%；The Ti3MC2Mass ratio with hydrofluoric acid is
(0.1~10): 1.
Preferably, the stirring rate being stirred to react is 50~500r/min；The time being stirred to react be 10~
1000min。
Preferably, step S1) in be stirred to react after carry out centrifugal treating；The centrifugation rate of the centrifugal treating be 100~
10000r/min。
Preferably, the step S2) in heat temperature be 100 DEG C~500 DEG C.
Preferably, the cryogenic liquid is one of liquid helium, liquid nitrogen and liquid argon or a variety of.
Preferably, the step S2) specifically:
Powder after the etching is heated, is then contacted with cryogenic liquid, repeats the above steps 0~20 time, obtains
To intermediate.
Preferably, the step S3) in be ultrasonically treated ultrasonic power be 10~1000W；The time of the ultrasonic treatment
For 1~100min.
The present invention also provides a kind of Ti of above method preparation3C2Nanometer sheet.
The present invention provides a kind of removing Ti3C2The method of nanometer sheet, comprising: S1) by Ti3MC2It mixes, stirs with hydrofluoric acid
Powder after mixing reaction, after being etched；The M is Al, Si or Ge；S2) powder after the etching is heated, then
It is contacted with cryogenic liquid, obtains intermediate；S3 the intermediate is ultrasonically treated in water), obtains Ti3C2Nanometer sheet.With
The prior art is compared, and the present invention uses cryogenic liquid for medium, and using it, fast vaporizing green removes two dimension Ti at high temperature3C2
Nanometer sheet, stripping means implementing process is simple, process is controllable, has stronger promotion and application value, and do not use dimethyl
The toxicity organic reagent such as sulfoxide or dimethylformamide, realizes green removing, and sonication treatment time also greatly shortens, and low energy consumption,
Belong to environmentally friendly chemical preparation process, meets the preparation trend of current low energy consumption.
Detailed description of the invention
Fig. 1 is Ti used in the embodiment of the present invention 13AlC2The stereoscan photograph of powder raw material；
Fig. 2 is Ti used in the embodiment of the present invention 13AlC2The EDS energy spectrum diagram of powder raw material；
Fig. 3 is Ti obtained in step 1.2 in the embodiment of the present invention 13C2The stereoscan photograph of powder；
Fig. 4 is Ti obtained in step 1.2 in the embodiment of the present invention 13C2The EDS energy spectrum diagram of powder；
Fig. 5 is two dimension Ti obtained in step 1.5 in the embodiment of the present invention 13C2The stereoscan photograph of nanometer sheet；
Fig. 6 is two dimension Ti obtained in step 2.5 in the embodiment of the present invention 23C2The stereoscan photograph of nanometer sheet；
Fig. 7 is two dimension Ti obtained in step 3.5 in the embodiment of the present invention 33C2The stereoscan photograph of nanometer sheet；
Fig. 8 is two dimension Ti obtained in step 4.5 in the embodiment of the present invention 43C2The stereoscan photograph of nanometer sheet；
Fig. 9 is two dimension Ti obtained in step 5.5 in the embodiment of the present invention 53C2The stereoscan photograph of nanometer sheet；
Figure 10 is two dimension Ti obtained in step 6.5 in the embodiment of the present invention 63C2The stereoscan photograph of nanometer sheet；
Figure 11 is two dimension Ti obtained in step 7.5 in the embodiment of the present invention 73C2The stereoscan photograph of nanometer sheet.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of removing Ti3C2The method of nanometer sheet, comprising:
S1) by Ti3MC2It is mixed with hydrofluoric acid, the powder after being stirred to react, after being etched；The M is Al, Si or Ge；
S2) powder after the etching is heated, is then contacted with cryogenic liquid, intermediate is obtained；
S3 the intermediate is ultrasonically treated in water), obtains Ti3C2Nanometer sheet.
The present invention is not particularly limited the source of all raw materials, is commercially available.
Wherein, the Ti3MC2For Ti well known to those skilled in the art3MC2Powder has no special limitation,
In the present invention preferably its having a size of 500~20000nm；The M is Al, Si or Ge, in the present invention preferably Al.
By Ti3MC2It is mixed with hydrofluoric acid；The hydrofluoric acid is hydrofluoric acid well known to those skilled in the art, has no spy
Different limitation, the mass concentration of heretofore described hydrofluoric acid are preferably 30%~60%, and more preferably 35%~55%, then it is excellent
It is selected as 40%~50%, most preferably 40%；The Ti3MC2Mass ratio with hydrofluoric acid is preferably (0.1~10): 1, more preferably
For (0.1~8): 1, be further preferably (0.1~5): 1, it is further preferably (1~3): 1, most preferably (1~2): 1.
After mixing, it is stirred to react；It is described to be stirred to react preferably magnetic agitation reaction and/or mechanical agitator stirring instead
It answers；The stirring rate being stirred to react is preferably 50~500r/min, more preferably 100~400r/min, is further preferably 200
~300r/min, most preferably 200r/min；The time being stirred to react is preferably 10~1000min, more preferably 50~
800min is further preferably 100~500min, is further preferably 100~300min, is further preferably 150~250min, most preferably
180~200min.
After being stirred to react, centrifugal treating is preferably carried out；The centrifugation rate of the centrifugal treating is preferably 100~10000r/
Min, more preferably 500~7500r/min are further preferably 1000~5000r/min, are further preferably 3000~5000r/min, most
Preferably 4000r/min.
After centrifugal treating, sediment is collected, preferably sediment is started the cleaning processing and is dried, after being etched
Powder；The cleaning treatment preferably uses deionized water to carry out；The number of the cleaning treatment is preferably 1~8 time, more preferably
2~6 times, be further preferably 3~5 times, most preferably 4 times；The drying method is method well known to those skilled in the art
, special limitation is had no, is preferably dried in the present invention；The temperature of the drying process is preferably 50 DEG C~150 DEG C, more
Preferably 80 DEG C~120 DEG C, be further preferably 90 DEG C~110 DEG C, most preferably 100 DEG C；The time of the drying process is preferably
10~50h, more preferably 10~40h are further preferably 20~30h, most preferably for 24 hours.
The powder after obtained etching after drying process is to contain organ shape Ti3C2Mixture；Organ in the mixture
Shape Ti3C2Quality be preferably no less than 40%.
Powder after the etching is heated, is preferably heated to 100 DEG C~500 DEG C, be more preferably heated to 200 DEG C~
500 DEG C, 300 DEG C~500 DEG C are further preferably heated to, is most preferably heated to 400 DEG C；Then it is contacted with cryogenic liquid；The low temperature
Liquid is cryogenic liquid well known to those skilled in the art, has no special limitation, is preferably liquid helium, liquid nitrogen in the present invention
With one of liquid argon or a variety of；Cooled down with cryogenic liquid to the powder after the etching of heating in the present invention, while in powder
Body surface vaporization；The method of the contact is method well known to those skilled in the art, has no special limitation, the present invention
In preferably follow the steps below: by after heating etch after powder be placed in glass container, funnel is inserted into the glass
Vessel port, and using polymeric foam, it is preferable to use glass container mouth is stated in porous polyimide foam plugs residence, by funnel to
Cryogenic liquid is added in glass container.
It is preferably repeated above-mentioned the step of preferably repeating above-mentioned heating and be in contact with cryogenic liquid to improve peeling effect
Step 0~20 time, it is more preferably repeatedly 5~20 times, further preferably repeatedly 10~20 times, further preferably repeatedly 15~20 times, most preferably heavy
It is 20 times multiple, obtain intermediate.
The intermediate is ultrasonically treated in water；The mass ratio of the intermediate and water be preferably 1:(100~
5000), more preferably 1:(500~3000), be further preferably 1:(1000~2000), most preferably 1:1000；At the ultrasound
The ultrasonic power of reason is preferably 10~1000W, more preferably 100~1000W, is further preferably 100~800W, is further preferably 200
~600W, most preferably 200~400W；The time of the ultrasonic treatment is preferably 1~100min, more preferably 1~80min,
It is further preferably 1~60min, is further preferably 1~30min, is further preferably 10~30min, most preferably 15~20min.
After ultrasonic treatment, preferably it is centrifuged；The rate of the centrifugation is preferably 100~8000r/min, more preferably
200~5000r/min is further preferably 500~5000r/min, is further preferably 1000~4000r/min, most preferably 3000~
4000r/min。
After centrifugation, the supernatant liquor preferably obtained to centrifugation is filtered；The method of the filtering is those skilled in the art
Method known to member has no special limitation, preferably filters in the present invention；The filtering preferably uses polyethersulfone membranes
It carries out.
After filtering, preferably it is dried；The method of the drying is method well known to those skilled in the art, is had no
Special limitation, the present invention in preferably 50 DEG C~150 DEG C, more preferably 80 DEG C~120 DEG C, be further preferably 90 DEG C~110 DEG C,
Most preferably 100 DEG C；The time of the drying process is preferably 10~50h, more preferably 10~40h, further preferably for 20~
30h, most preferably for 24 hours.
The present invention also provides a kind of Ti of above method preparation3C2Nanometer sheet；The Ti3C2The thickness of nanometer sheet is preferred
For 10~1000nm；The Ti3C2The thickness of nanometer sheet is preferably 100~5000nm；The Ti3C2The thickness of nanometer sheet is preferred
For 100~5000nm.
The present invention uses cryogenic liquid for medium, and using it, fast vaporizing green removes two dimension Ti at high temperature3C2Nanometer
Piece, stripping means implementing process is simple, process is controllable, has stronger promotion and application value, and do not use dimethyl sulfoxide
Or the toxicity organic reagent such as dimethylformamide, green removing is realized, sonication treatment time also greatly shortens, and low energy consumption, belongs to
Environmentally friendly chemical preparation process meets the preparation trend of current low energy consumption.
In order to further illustrate the present invention, lower to a kind of environmentally friendly and energy consumption provided by the invention with reference to embodiments
Remove Ti3C2The method of nanometer sheet is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
1.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time be 3 hours.
1.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
1.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 400 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
1.4 repeat the operating process of step 1.3 0 time.
1.5 by step 1.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 15min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to Ti3AlC2Powder raw material is analyzed, and obtains its stereoscan photograph, such as
Shown in Fig. 1.
Using X-ray energy spectrometer to Ti3AlC2Powder raw material is analyzed, and obtains its EDS energy spectrum diagram, as shown in Figure 2.
Using scanning electron microscope (SEM) to Ti obtained in step 1.23C2Powder is analyzed, its scanning electricity is obtained
Mirror photo, as shown in Figure 3.
Using X-ray energy spectrometer to Ti obtained in step 1.23C2Powder is analyzed, its EDS energy spectrum diagram is obtained, and is such as schemed
Shown in 4.
By FIG. 1 to FIG. 4 it is found that major part Ti3AlC2Blocky-shaped particle has been etched to the stacking lamellar of accordion shape.It is right
Than the constituency the EDS power spectrum before the constituency the EDS power spectrum and etching after etching, aluminium element content is greatly reduced, and illustrates hydrofluoric acid pair
Ti3AlC2The etching effect of aluminium element is very good in powder.
Using scanning electron microscope (SEM) to two dimension Ti obtained in embodiment 1.53C2Nanometer sheet, as shown in figure 5, aobvious
Show the limellar stripping poor effect for not repeating step 1.3, most of is all still in accordion shape.
Embodiment 2
2.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time be 3 hours.
2.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
2.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 400 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
2.4 are repeated 5 times the operating process of step 2.3.
2.5 by step 2.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 15min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to two dimension Ti obtained in 2.53C2Nanometer sheet is analyzed, its scanning is obtained
Electromicroscopic photograph, as shown in fig. 6, the limellar stripping that step 2.3 is only repeated 5 times by display is ineffective, most of is still in accordion
Shape stacking lamella.
Embodiment 3
3.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time be 3 hours.
3.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
3.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 400 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
3.4 are repeated 20 times the operating process of step 3.3.
3.5 by step 3.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio says and is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 15min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to two dimension Ti obtained in 3.53C2Nanometer sheet is analyzed, its scanning is obtained
Electromicroscopic photograph is as shown in Figure 7.Fig. 7 display works well by being repeated 20 times the limellar stripping of step 3.3 operation, accordion shape
Stacking lamellar Ti3C2It is stripped into the two-dimentional Ti of a great amount of high specific surface area3C2Lamella.
Embodiment 4
4.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time be 3 hours.
4.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
4.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 100 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
4.4 are repeated 20 times the operating process of step 4.3.
4.5 by step 4.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 15min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to two dimension Ti obtained in 4.53C2Nanometer sheet is analyzed, it obtains it and sweeps
Electromicroscopic photograph is retouched, as shown in figure 8, display major part Ti3C2It is still in accordion shape, peeling effect is bad.
Embodiment 5
5.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time be 3 hours.
5.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
5.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 500 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
5.4 are repeated 20 times the operating process of step 5.3.
5.5 by step 5.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 15min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to two dimension Ti obtained in 5.53C2Nanometer sheet is analyzed, its scanning is obtained
Electromicroscopic photograph, as shown in figure 9, the limellar stripping that display is repeated 20 times step 5.3 operation works well, accordion shape stacking
Lamellar Ti3C2It is stripped into a large amount of two dimension Ti3C2Lamella, but due in step 5.3 excessive temperature differentials lead to a large amount of two dimension Ti3C2
Lamella is broken.
Embodiment 6
6.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time 10min.
6.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
6.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 400 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
6.4 are repeated 20 times the operating process of step 6.3.
6.5 by step 6.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 15min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to two dimension Ti obtained in 6.53C2Nanometer sheet is analyzed, its scanning is obtained
Electromicroscopic photograph shows that most of particle is still in bulk, etching effect is bad as shown in Figure 10.
Embodiment 7
7.1 by Ti3AlC2Powder is placed in the plastic beaker on magnetic stirring apparatus, by Ti3AlC2Powder and hydrofluoric acid matter
The hydrofluoric acid that concentration is 40wt% is added into same beaker than being 1:10 for amount, sets 200r/min for stirring rotor speed, and
After start to stir, mixing time be 3 hours.
7.2 pour into the solution after etching in centrifuge tube, and then revolving speed is set as 4000r/min centrifugal treating, take precipitating
Object is added deionized water into sediment and cleans for filtering, and repeated washing 4 times, then by solid phase powder in 100 DEG C of environment temperature
The lower lasting drying in heating 24 hours of degree, obtains the lamellar Ti of stacking3C2Powder.
7.3 by Ti3C2Powder is put into glass beaker, then fills in porous polyimide foam in beaker mouth, and in foam
Upper opening is inserted into funnel, pours into 20ml liquid nitrogen into funnel immediately after beaker is heated to 400 DEG C on warm table, complete to liquid nitrogen
Continuous heating again after full vaporization.
7.4 are repeated 20 times the operating process of step 7.3.
7.5 by step 7.4, treated that powder is cooled to room temperature, then by powder and deionized water quality ratio 1:1000
Ratio is ultrasonically treated after powder is put into deionized water, ultrasonic power 200W, ultrasonic time 1min, after 4000r/
The centrifugal treating of min takes supernatant, then filters supernatant by polyethersulfone membranes to obtain powdered sample, then at 100 DEG C
Drying, obtains two-dimentional Ti3C2Lamella is completed.
Using scanning electron microscope (SEM) to two dimension Ti obtained in 7.53C2Nanometer sheet is analyzed, its scanning is obtained
Electromicroscopic photograph shows major part Ti as shown in figure 113C2It is still in accordion shape, peeling effect is bad.
Claims (10)
1. a kind of removing Ti3C2The method of nanometer sheet characterized by comprising
S1) by Ti3MC2It is mixed with hydrofluoric acid, the powder after being stirred to react, after being etched；The M is Al, Si or Ge；
S2) powder after the etching is heated, is then contacted with cryogenic liquid, intermediate is obtained；
S3 the intermediate is ultrasonically treated in water), obtains Ti3C2Nanometer sheet.
2. the method according to claim 1, wherein the Ti3MC2Size be 500~20000nm.
3. the method according to claim 1, wherein the mass concentration of the hydrofluoric acid is 30%~60%；Institute
State Ti3MC2Mass ratio with hydrofluoric acid is (0.1~10): 1.
4. the method according to claim 1, wherein the stirring rate being stirred to react is 50~500r/
min；The time being stirred to react is 10~1000min.
5. the method according to claim 1, wherein step S1) in be stirred to react after carry out centrifugal treating；It is described
The centrifugation rate of centrifugal treating is 100~10000r/min.
6. the method according to claim 1, wherein the step S2) in the temperature that heats be 100 DEG C~500
℃。
7. the method according to claim 1, wherein the cryogenic liquid is one in liquid helium, liquid nitrogen and liquid argon
Kind is a variety of.
8. the method according to claim 1, wherein the step S2) specifically:
It powder after the etching is heated, is then contacted with cryogenic liquid, repeats the above steps 0~20 time, obtain
Mesosome.
9. the method according to claim 1, wherein the step S3) in the ultrasonic power that is ultrasonically treated be 10
~1000W；The time of the ultrasonic treatment is 1~100min.
10. a kind of removing Ti described in any one of claim 1 to 93C2The Ti of the method preparation of nanometer sheet3C2Nanometer sheet.
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