CN105600760B - A kind of small size black phosphorus piece and preparation method thereof - Google Patents
A kind of small size black phosphorus piece and preparation method thereof Download PDFInfo
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- CN105600760B CN105600760B CN201510991279.9A CN201510991279A CN105600760B CN 105600760 B CN105600760 B CN 105600760B CN 201510991279 A CN201510991279 A CN 201510991279A CN 105600760 B CN105600760 B CN 105600760B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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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 invention provides a kind of preparation method of small size black phosphorus piece, including：In the case where completely cutting off air, take black phosphorus to be ground, and the black phosphorus after grinding is dispersed in the first organic solvent, obtain the dispersion liquid that concentration is 0.6~1.2mg/mL；The dispersion liquid is first subjected to probe-type ultrasound 2~4 hours in the case where power is 1000~1400W, then carries out water bath sonicator 8~12 hours in the case where power is 200~400W；After ultrasound, supernatant is collected in centrifugation, and the supernatant is the small size black phosphorus piece after peeling off.This method technique is simple to operation, and yield is higher, favorable reproducibility, easily realizes the inexpensive industrialization production of small size black phosphorus piece, and does not produce secondary pollution problem to environment.Present invention also offers a kind of small size black phosphorus piece.
Description
Technical field
The present invention relates to field of nanometer material technology, more particularly to a kind of small size black phosphorus piece and preparation method thereof.
Background technology
Black phosphorus, there is natural pleated structures similar but different from graphene film Rotating fields, this unique pleated structure
It result in black phosphorus and possess many unique physical properties, as black phosphorus possesses the unexistent semiconductor gap of graphene and is direct band
In same position at the top of gap, i.e. electronic conduction energy band (conduction band) bottom and non-conductive energy band (valence band), realize and led from non-conductive
Electricity, electronic values need absorbability, it means that black phosphorus can be used as variable semiconductor, can be included with light with direct-coupling, spectrum
Whole visible ray is near infrared region.Therefore, black phosphorus has wide application in fields such as nano optoelectronics, biomedicines
Prospect, such as：Photoelectric device, sensor, switch etc..And the two-dimentional black phosphorus lamellar structure of reduced size is in optical markings, photoelectron
Device etc. has more very big application prospect, and therefore, reduced size black phosphorus piece prepares great realistic meaning.
At present, method (such as adhesive tape tears point-score), chemical vapour deposition technique technology are by mechanically pulling off, scholars are
Prepare the black phosphorus material of sheet.But the yield of the sheet black phosphorus of mechanical stripping method preparation is relatively low, be not suitable for being used for manufacturer
Industry application material, and it is cumbersome, time-consuming, obtained scantling is larger, more in micron order；And chemical vapour deposition technique
The amount of the black phosphorus piece of preparation is considerably less, and is not easy to repeat.Therefore, it is badly in need of developing a kind of extensive preparation small size black phosphorus piece
Method.
The content of the invention
In view of this, the invention provides a kind of small size black phosphorus piece and preparation method thereof, the preparation method will be by that will visit
Pin ultrasound and water bath sonicator are combined, and by the stripping to act synergistically to realize to black phosphorus block, acquisition monodispersity is good, size
Homogeneous small size black phosphorus piece, the lateral dimension of obtained small size black phosphorus piece about in 1~3nm, longitudinal size 0.8~
2nm, size is smaller, and it shows obvious absorption characteristic in ultraviolet-visible region.The method technique is simple to operation, production
Rate is higher, favorable reproducibility, easily realizes inexpensive industrialization production and does not produce secondary pollution problem to environment.
In a first aspect, the invention provides a kind of preparation method of small size black phosphorus piece, comprise the following steps：
(1) under anaerobic, black phosphorus is taken, the particle diameter of the black phosphorus is 5~50 μm, and the black phosphorus is dispersed in into first has
In solvent, dispersion liquid is obtained, concentration of the black phosphorus in the dispersion liquid is 0.6~1.2 mg/mL；
(2) dispersion liquid is first subjected to probe-type ultrasound 1~4 hour in the case where power is 1000~1400W, then in work(
Rate is water bath sonicator to be carried out under 100~400W 8~12 hours；
(3) after ultrasound, centrifugation, supernatant is collected, obtains small size black phosphorus piece.
Preferably, the lateral dimension of the small size black phosphorus piece is in 1~3nm.
Preferably, the longitudinal size of the small size black phosphorus piece is in 0.8~2nm.
Preferably, the black phosphorus is by the way that black phosphorus block to be ground to obtain.
More preferably, it is preferable that the black phosphorus block is converted and formed under High Voltage and high-temperature using white phosphorus.
Preferably, first organic solvent includes 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), two
One kind in methyl sulfoxide (DMSO), acetone, tetrahydrofuran, absolute ethyl alcohol, methanol, isopropanol, chloroform and dichloromethane
It is or a variety of.
It is highly preferred that first organic solvent is absolute ethyl alcohol.The absolute ethyl alcohol can be with the black phosphorus block after grinding
Stripping, obtained small size black phosphorus piece in ethanol, can be with the good intermiscibility of water, can be by prepared small size black phosphorus
Piece is used in water miscible system.
Preferably, the ultrasonic and described water bath sonicator of the probe-type is completed under condition of ice bath.
It is further preferred that the temperature of the ice bath is less than 4 DEG C.
As described in the present invention, the condition of ice bath, refer to during the ultrasonic and described water bath sonicator of the probe-type,
Container equipped with black phosphorus dispersion liquid is placed in another container equipped with ice cube (such as beaker, test tube).
Preferably, the power of the probe-type ultrasound is 1000~1150W.
It is further preferred that the power of the probe-type ultrasound is 1000~1100W.
Preferably, the power of the probe-type ultrasound is 1250~1400W.
It is further preferred that the power of the probe-type ultrasound is 1300~1400W.
Preferably, the time of the probe-type ultrasound is 1~2.5 hour.
Preferably, the time of the probe-type ultrasound is 3.1~4 hours.
In the embodiment of the present invention, the power of probe-type ultrasound can be 1000W, 1100W, 1150W, 1200W,
1250W、1300W、1350W、1400W；The time of probe-type ultrasound can be 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h.
Preferably, the power of the water bath sonicator is 100~280W.
It is further preferred that the power of the water bath sonicator is 100~200W.
Preferably, the power of the water bath sonicator is 320~400W.
Preferably, the time of the water bath sonicator is 8-9.5h.
Preferably, the time of the water bath sonicator is 10.5-12h.
In the embodiment of the present invention, the power of the water bath sonicator can be 100W, 150W, 200W, 250 W, 280W,
300W、310W、320W、350W、400W；Probe-type ultrasound time can be 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h,
11.5h、12h。
Preferably, the rotating speed of the centrifugation is 5000~9000 revs/min, and centrifugation time is 15~25 minutes.
Preferably, in step (3), the centrifugation is carried out under the protection of glove box nitrogen.
As described in the present invention, other operations in the present invention in addition to probe-type ultrasound and water bath sonicator are in anaerobic bar
Part is carried out, and is preferably carried out under the protection of glove box nitrogen.
Preferably, the step (3) also includes：
After the collection supernatant, high speed centrifugation is carried out to the supernatant, collects solid product or will be described solid
Body product is distributed in the second organic solvent, obtains small size black phosphorus piece.
Preferably, the ultracentrifugal rotating speed is 10000-15000rpm.
Preferably, second organic solvent includes 1-METHYLPYRROLIDONE (NMP), dimethylformamide (DMF), two
One or more in methyl sulfoxide (DMSO), acetone, tetrahydrofuran, absolute ethyl alcohol, methanol and isopropanol.
First organic solvent and second organic solvent, can be homogeneous solvent, or not homogeneous solvent.
The preparation method for the small size black phosphorus piece that first aspect present invention provides, probe sonication and water bath sonicator are combined
Liquid phase stripping method, by the stripping to act synergistically to realize to black phosphorus block, the method technique is simple to operation, yield compared with
Height, there is obvious advantage compared to current mechanical stripping method and chemical vapour deposition technique etc., the controllable single dispersing of size can be obtained
Good, size uniformity the small size black phosphorus piece of property, easily realizes inexpensive industrialization production.
Preparation method based on first aspect present invention, it is expected to realize from black phosphorus solid to the extensive of small size black phosphorus piece
Prepared by industrialization, laid the foundation for small size black phosphorus piece in the application of biomedical sector, optoelectronic areas.
Second aspect, present invention also offers small size black phosphorus piece after the stripping being prepared by above-mentioned preparation method.Institute
The lateral dimension of small size black phosphorus piece is stated in 1~3nm, longitudinal size is in 0.8~2nm.
The particle diameter distribution of obtained small size black phosphorus piece is narrower, and size is smaller, and its band gap increased, it is ultraviolet-can
See that light region shows obvious absorption characteristic, can apply to prepare photo-thermal therapy medicine, optical markings medicine, sensor etc.
Biomedical frontier field.
The advantages of embodiment of the present invention, will partly illustrate in the following description, a part according to specification be it is aobvious and
It is clear to, or can be known by the implementation of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 be small size black phosphorus piece made from the embodiment of the present invention 1 in 1-METHYLPYRROLIDONE solution it is ultraviolet-can
See-near-infrared absorption spectrum figure；
Fig. 2 is the low power transmission electron microscope picture (TEM) of small size black phosphorus piece made from the embodiment of the present invention 1；
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) figure of small size black phosphorus piece made from the embodiment of the present invention 1；
Fig. 4 is the low power transmission electron microscope picture of small size black phosphorus piece made from the embodiment of the present invention 4；
Fig. 5 is AFM (AFM) figure of small size black phosphorus piece made from the embodiment of the present invention 4；
Fig. 6 is the size statistic figure carried out for lines in Fig. 51,2,3；
Fig. 7 is the low power transmission electron microscope picture of black phosphorus piece made from comparative example 1；
Fig. 8 is the low power transmission electron microscope picture of black phosphorus piece made from comparative example 2.
Embodiment
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of principle of the embodiment of the present invention is not departed from, some improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to
Under specific embodiment.In the range of constant principal right, can be suitably carry out change implementation.
In the embodiment of the present invention, the black phosphorus block is bought from Smart-Elements companies.
Instrument used in the probe-type ultrasound is thinner than the BILON-1800Y type ultrasonic waves of bright Instrument Ltd. for Shanghai
Born of the same parents' crusher, the instrument used in the water bath sonicator are the KQ-300DE type numerical controls of Kunshan Ultrasonic Instruments Co., Ltd.'s production
Ultrasonic washing instrument.
Embodiment 1
A kind of preparation method of small size black phosphorus piece, comprises the following steps：
25mg black phosphorus block is weighed in the glove box of inflated with nitrogen, is milled and is distributed to 25mL N- methylpyrroles
Alkanone, sealing, obtains 1mg/ml dispersion liquid；Ultrasound 3 hours under 1200W probe sonication power, then followed by 300W work(
Water bath sonicator 10 hours under rate, whole ultrasonic procedure be all controlled by ice bath it is accomplished below in 277K；Then 7000 turns/
Centrifuged under minute rotating speed, centrifugation time is 20 minutes, takes supernatant liquor, obtains being dispersed in the small chi in 1-METHYLPYRROLIDONE
Very little black phosphorus piece.
The products therefrom of the present embodiment 1 is characterized, as a result as shown in FIG. 1 to 3, wherein, Fig. 1 is small size black phosphorus piece
UV-visible-near infrared absorption figure in 1-METHYLPYRROLIDONE solution；Fig. 2 is that the low power of small size black phosphorus piece is saturating
Penetrate electron microscope；Fig. 3 is the high-resolution-ration transmission electric-lens figure of small size black phosphorus piece.As can be seen from Figure 1：Small size black phosphorus piece exists
300-900nm regions show obvious absorption characteristic, and its absorption peak is about in 485nm, when this is smaller with the size of black phosphorus piece,
Its band gap increased relation；Fig. 2 illustrates that the monodispersity of obtained small size black phosphorus piece is good, size uniformity, its horizontal chi
It is very little in 2.6nm or so；The lattice fringe of black phosphorus thin slice atomic layer can be significantly seen from Fig. 3, wherein, spacing of lattice is
0.256nm corresponds to (111) crystal face of black phosphorus crystal.
Embodiment 2
A kind of preparation method of small size black phosphorus piece, comprises the following steps：
15mg black phosphorus block is weighed in the glove box of inflated with nitrogen, is milled and is distributed to 25mL N- crassitudes
Ketone, sealing, obtains 0.6mg/ml dispersion liquid；Ultrasound 1 hour under 1400W probe-type ultrasonic powers, then followed by 400W
Water bath sonicator 8 hours under power, whole ultrasonic procedure be all controlled by ice bath it is accomplished below in 277K；Then 5000
Centrifuged under rev/min rotating speed, centrifugation time is 20 minutes, takes supernatant liquor, obtains small size black phosphorus piece.
Embodiment 3
A kind of preparation method of small size black phosphorus piece, comprises the following steps：
30mg black phosphorus block is weighed in the glove box of inflated with nitrogen, is milled and is distributed in 25mL dimethyl sulfoxide (DMSO),
Sealing, obtains 1.2mg/ml dispersion liquid；Ultrasound 4 hours under 1000W probe-type ultrasonic powers, then followed by 100W work(
Water bath sonicator 12 hours under rate, whole ultrasonic procedure be all controlled by ice bath it is accomplished below in 277K；Then 9000 turns/
Centrifuged under minute rotating speed, centrifugation time is 10 minutes, takes supernatant liquor, obtains small size black phosphorus piece.
Embodiment 4
A kind of preparation method of small size black phosphorus piece, comprises the following steps：
25mg black phosphorus block is weighed in the case where completely cutting off air conditionses, is milled and is distributed in 25mL absolute ethyl alcohol,
1mg/mL dispersion liquid is obtained, is sealed；And then ultrasound 2 hours under 1000W probe-type ultrasonic powers, then in 300W power
Lower water bath sonicator 10 hours, whole ultrasonic procedure are all to control temperature by ice bath；Then under 8000 revs/min of rotating speeds from
The heart 20 minutes, takes supernatant liquor, obtains extra small black phosphorus nanometer sheet.
The products therefrom of the present embodiment 4 is characterized, as a result as shown in Fig. 4~Fig. 5, wherein, Fig. 4 is the embodiment of the present invention
The low power transmission electron microscope picture of small size black phosphorus piece made from 4；Fig. 5 is the original of small size black phosphorus piece made from the embodiment of the present invention 4
Sub- force microscope (AFM) figure.
As seen from Figure 4, the size uniformity of the small size black phosphorus piece, good dispersion, its lateral dimension are left in 2nm
The right side, than using 1-METHYLPYRROLIDONE make dispersant stir made from small size black phosphorus piece particle diameter it is smaller, this be probably by
Caused by its polarity.And AFM (AFM) is carried out to obtained small size black phosphorus piece and characterized, as a result as seen in figs. 5-6,
In Fig. 6 in abscissa " position " representative graph 5 each lines length, from fig. 5, it can be seen that the radial direction of the small size black phosphorus piece
Size is in 0.8-2nm or so.
Embodiment 5
A certain amount of black phosphorus block is weighed in the case where completely cutting off air conditionses, is milled and is distributed in appropriate absolute ethyl alcohol,
1.2mg/mL dispersion liquid is obtained, is sealed；Ultrasound 3 hours under 1400W probe-type ultrasonic powers, then followed by 300W power
Lower water bath sonicator 10 hours, whole ultrasonic procedure are all to control temperature by ice bath；Then under 9000 revs/min of rotating speeds from
The heart, centrifugation time are 20 minutes, take supernatant liquor, obtain extra small black phosphorus nanometer sheet.
Embodiment 6
A kind of preparation method of small size black phosphorus piece, comprises the following steps：
A certain amount of black phosphorus block is weighed in the case where completely cutting off air conditionses, is milled and is distributed in appropriate absolute ethyl alcohol,
0.8mg/mL dispersion liquid is obtained, is sealed；First ultrasound 3 hours under 1200W probe-type ultrasonic powers, then followed by 200W
Water bath sonicator 12 hours under power, whole ultrasonic procedure are all to control temperature by ice bath；Then 9000 revs/min of rotating speeds
Lower centrifugation 15 minutes, takes supernatant liquor, obtains extra small black phosphorus nanometer sheet.
For the technique effect of the prominent present invention, comparative example 1, comparative example 2 are now set respectively for embodiment 4.
Comparative example 1
A kind of preparation method of black phosphorus piece, comprises the following steps：
25mg black phosphorus block is weighed in the case where completely cutting off air conditionses, is milled and is distributed in 25mL absolute ethyl alcohol,
1mg/mL dispersion liquid is obtained, is sealed；And then ultrasound 2 hours under 1000W probe-type ultrasonic powers, whole ultrasonic procedure is all
It is that temperature is controlled by ice bath；Then centrifuged 20 minutes under 8000 revs/min of rotating speeds, take supernatant liquor, obtained extra small black
Phosphorus nanometer sheet.
Comparative example 2
A kind of preparation method of black phosphorus piece, comprises the following steps：
25mg black phosphorus block is weighed in the case where completely cutting off air conditionses, is milled and is distributed in 25mL absolute ethyl alcohol,
1mg/mL dispersion liquid is obtained, is sealed；And then water bath sonicator 10 hours under 300W power, whole ultrasonic procedure are all logical
Ice bath is crossed to control temperature；Then centrifuged 20 minutes under 8000 revs/min of rotating speeds, take supernatant liquor, obtained extra small black phosphorus and receive
Rice piece.
Fig. 7, Fig. 8 are respectively the transmission electron microscope picture for the black phosphorus piece that comparative example 1, comparative example 2 are prepared.By scheming
7 understand, when only carrying out probe-type supersound process to being dispersed with the organic solvent of black phosphorus block after grinding, black phosphorus mainly with compared with
Thin large stretch of presence, for size about in 200nm, this indicates that probe-type ultrasound only is only capable of effectively destroying between black phosphorus piece
Interaction, but can not realize its transformation to small size nanometer sheet；It is corresponding when it is handled in only water bath sonicator,
As shown in figure 8, the size of obtained sample, about in tens rans, this shows that water bath sonicator can be played effectively to black
The cutting of phosphorus piece, the effect for making its size diminish.In addition, it is clearly visible when only with probe-type ultrasound or only with water bath sonicator
When, the agglomeration of products obtained therefrom can not obtain good monodispersity, size uniformity, lateral dimension and be received several at all than more serious
The small size black phosphorus piece of rice.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (6)
1. a kind of preparation method of small size black phosphorus piece, it is characterised in that comprise the following steps：
(1) under anaerobic, black phosphorus is taken, the particle diameter of the black phosphorus is 5~50 μm, and it is organic molten that the black phosphorus is dispersed in into first
In agent, dispersion liquid is obtained, concentration of the black phosphorus in the dispersion liquid is 0.6~1.2mg/mL, wherein, described first is organic
Solvent is absolute ethyl alcohol；
(2) dispersion liquid is first subjected to probe-type ultrasound 1~4 hour in the case where power is 1000~1150W, is then in power
Water bath sonicator is carried out under 100~400W 8~12 hours；
(3) after ultrasound, centrifugation, supernatant is collected, obtains small size black phosphorus piece.
2. preparation method as claimed in claim 1, it is characterised in that the black phosphorus is by the way that black phosphorus block is ground
Arrive.
3. preparation method as claimed in claim 1, it is characterised in that the lateral dimension of the small size black phosphorus piece 1~
3nm。
4. preparation method as claimed in claim 1, it is characterised in that the power of the water bath sonicator is 100~280W.
5. preparation method as claimed in claim 1, it is characterised in that the ultrasonic and described water bath sonicator of the probe-type be
Completed under condition of ice bath, the temperature of the ice bath is less than 4 DEG C.
6. preparation method as claimed in claim 1, it is characterised in that the rotating speed of the centrifugation is 5000~9000 revs/min,
Centrifugation time is 15~25 minutes.
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