CN105600760A - Small-sized black phosphorus flakes and preparation method thereof - Google Patents
Small-sized black phosphorus flakes and preparation method thereof Download PDFInfo
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- CN105600760A CN105600760A CN201510991279.9A CN201510991279A CN105600760A CN 105600760 A CN105600760 A CN 105600760A CN 201510991279 A CN201510991279 A CN 201510991279A CN 105600760 A CN105600760 A CN 105600760A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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 preparation method of small-sized black phosphorus flakes. The preparation method comprises the following steps: under the condition that air is isolated, grinding black phosphorus, and dispersing the ground black phosphorus into a first organic solvent to obtain a dispersion at the concentration of 0.6-1.2mg/mL; performing probe-type ultrasonic treatment to the dispersion for 2-4h under the power of 1000-1400W first and then performing water-bath ultrasonic treatment for 8-12h under the power of 200-400W; after the ultrasonic treatment, centrifuging and collecting a supernatant, namely the stripped small-sized black phosphorus flakes. The preparation method is simple in process, easy to operate, relatively high in yield, good in reproducibility, easy to realize low-cost industrial production of the small-sized black phosphorus flakes, and free of secondary pollution to the environment. The invention further provides the small-sized black phosphorus flakes.
Description
Technical field
The present invention relates to novel nano-material field, particularly relate to a kind of small size black phosphorus sheet and preparation side thereofMethod.
Background technology
Black phosphorus, has similar but is different from the natural pleated structure of graphene sheet layer structure, the pleat of this uniquenessWrinkle structure has caused black phosphorus to have the physical property of many uniquenesses, and as black phosphorus possesses, Graphene is unexistent partly leadsBody space and be direct band gap, electronic conduction can be with (conduction band) bottom and non-conductive can top by band (valence band)Portion, at same position, realizes from non-conductive conduction, and electronic values needs absorbability, this means that black phosphorus canAs variable semiconductor, can direct-coupling with light, spectrum has comprised that whole visible ray is near infrared region.Therefore, the fields such as black phosphorus is learned at nano photoelectric, biomedicine have broad application prospects, as: photoelectricityDevice, sensor, switch etc. And the two-dimentional black phosphorus lamellar structure of reduced size is at optical markings, photoelectronThe aspects such as device have more very large application prospect, and therefore, the preparation of reduced size black phosphorus sheet has reality meaningJustice.
At present, by technology such as mechanical stripping method (as adhesive tape tears point-score), chemical vapour deposition techniques,Scholars have prepared the black phosphorus material of sheet. But, the productive rate of the standby sheet black phosphorus of mechanical stripping legal systemLower, be not suitable for for production commercial applicability material, and complex operation, length consuming time, the material chi that obtainsVery little larger, how at micron order; And the amount of black phosphorus sheet prepared by chemical vapour deposition technique is considerably less, and be difficult for heavyMultiple. Therefore, be badly in need of developing a kind of extensive method of preparing small size black phosphorus sheet.
Summary of the invention
In view of this, the invention provides a kind of small size black phosphorus sheet and preparation method thereof, this preparation method passes throughBy ultrasonic probe and water-bath is ultrasonic combines,, obtain to realize the peeling off of black phosphorus block by synergyMonodispersity is good, the small size black phosphorus sheet of size homogeneous, and the lateral dimension of prepared small size black phosphorus sheet approximatelyAt 1～3nm, longitudinal size is at 0.8～2nm, and size is less, and it presents bright in ultraviolet-visible regionAobvious absorption characteristic. The method technique is simple to operation, and productive rate is higher, favorable reproducibility, easily realizes low costIndustrialization is produced and environment is not produced to secondary pollution problem.
First aspect, the invention provides a kind of preparation method of small size black phosphorus sheet, comprises the following steps:
(1) under oxygen free condition, get black phosphorus, the particle diameter of described black phosphorus is 5～50 μ m, and described black phosphorus is dividedBe dispersed in the first organic solvent, obtain dispersion liquid, the concentration of described black phosphorus in described dispersion liquid is 0.6～1.2mg/mL；
(2) be first under 1000～1400W, to carry out probe-type ultrasonic 1～4 hour at power by described dispersion liquid,Then be under 100～400W, to carry out water-bath ultrasonic 8～12 hours at power;
(3) after ultrasonic, centrifugal, collect supernatant, obtain small size black phosphorus sheet.
Preferably, the lateral dimension of described small size black phosphorus sheet is at 1～3nm.
Preferably, the longitudinal size of described small size black phosphorus sheet is at 0.8～2nm.
Preferably, described black phosphorus is by black phosphorus block is ground and obtained.
More preferably, preferably, described black phosphorus block be utilize white phosphorus to transform under High Voltage and high-temperature andForm.
Preferably, described the first organic solvent comprises 1-METHYLPYRROLIDONE (NMP), dimethyl formamide(DMF), dimethyl sulfoxide (DMSO) (DMSO), acetone, oxolane, absolute ethyl alcohol, methyl alcohol, isopropyl alcohol,One or more in chloroform and carrene.
More preferably, described the first organic solvent is absolute ethyl alcohol. Described absolute ethyl alcohol can with grind after blackPeeling off of phosphorus block, the small size black phosphorus sheet making in ethanol, can with the good intermiscibility of water, can be byPrepared small size black phosphorus sheet is for water miscible system.
Preferably, the ultrasonic and described water-bath of described probe-type is ultrasonic is all to complete under condition of ice bath.
Further preferably, the temperature of described ice bath is below 4 DEG C.
As described in the present invention, described condition of ice bath, refers to ultrasonic in described probe-type and described water-bath is ultrasonicIn process, the container that black phosphorus dispersion liquid is housed is placed in to another container (as beaker, test tube) that ice cube is housedIn.
Preferably, the ultrasonic power of described probe-type is 1000～1150W.
Further preferably, the ultrasonic power of described probe-type is 1000～1100W.
Preferably, the ultrasonic power of described probe-type is 1250～1400W.
Further preferably, the ultrasonic power of described probe-type is 1300～1400W.
Preferably, the ultrasonic time of described probe-type is 1～2.5 hour.
Preferably, the ultrasonic time of described probe-type is 3.1～4 hours.
In the embodiment of the present invention, the ultrasonic power of described probe-type can be 1000W, 1100W, 1150W,1200W, 1250W, 1300W, 1350W, 1400W; The ultrasonic time of probe-type can be 1h,1.5h、2h、2.5h、3h、3.5h、4h。
Preferably, the ultrasonic power of described water-bath is 100～280W.
Further preferably, the ultrasonic power of described water-bath is 100～200W.
Preferably, the ultrasonic power of described water-bath is 320～400W.
Preferably, the ultrasonic time of described water-bath is 8-9.5h.
Preferably, the ultrasonic time of described water-bath is 10.5-12h.
In the embodiment of the present invention, the ultrasonic power of described water-bath can be 100W, 150W, 200W, 250W, 280W, 300W, 310W, 320W, 350W, 400W; Ultrasonic time of probe-type is passableFor 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h.
Preferably, described centrifugal rotating speed is 5000～9000 revs/min, and centrifugation time is 15～25 minutes.
Preferably, in step (3), described centrifugal be to carry out under glove box nitrogen protection.
As described in the present invention, in the present invention except ultrasonic other of the ultrasonic and water-bath of probe-type operate be allOxygen free condition carries out, and preferably under glove box nitrogen protection, carries out.
Preferably, described step (3) also comprises:
After described collection supernatant, described supernatant is carried out to high speed centrifugation, collect solid product or incite somebody to actionDescribed solid product is distributed in the second organic solvent, obtains small size black phosphorus sheet.
Preferably, described ultracentrifugal rotating speed is 10000-15000rpm.
Preferably, described the second organic solvent comprises 1-METHYLPYRROLIDONE (NMP), dimethyl formamide(DMF), in dimethyl sulfoxide (DMSO) (DMSO), acetone, oxolane, absolute ethyl alcohol, methyl alcohol and isopropyl alcoholOne or more.
Described the first organic solvent and described the second organic solvent, can be homogeneous solvent, can be also differentPlant solvent.
The preparation method of the small size black phosphorus sheet that first aspect present invention provides, by ultrasonic probe and the ultrasonic phase of water-bathIn conjunction with liquid phase stripping method, by synergy, to realize the peeling off of black phosphorus block, the method technique is simpleEasy to operate, productive rate is higher, and comparing current mechanical stripping method and chemical vapour deposition technique etc. has obvious advantage,Can obtain that the controlled monodispersity of size is good, the small size black phosphorus sheet of size homogeneous, easily realize low cost industryChange and produce.
Based on the preparation method of first aspect present invention, be expected to realize large from black phosphorus solid to small size black phosphorus sheetScale industrialization preparation, for small size black phosphorus sheet is established base in the application of biomedical sector, optoelectronic areasPlinth.
Second aspect, the present invention also provides the rear small size black phosphorus of peeling off being prepared by above-mentioned preparation methodSheet. The lateral dimension of described small size black phosphorus sheet is at 1～3nm, and longitudinal size is at 0.8～2nm.
The particle diameter narrow distribution of prepared small size black phosphorus sheet, size is less, and its band gap increases to some extent,Ultraviolet-visible light region list reveals obvious absorption characteristic, can be applied to and prepare photo-thermal therapy medicine, opticsLabeled drug, sensor biomedical frontier field.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part according to description isApparent, or can know by the enforcement of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 is the purple of the small size black phosphorus sheet that makes of the embodiment of the present invention 1 in 1-METHYLPYRROLIDONE solutionOutward-Visible-to-Near InfaRed abosrption spectrogram;
Fig. 2 is the low power transmission electron microscope picture (TEM) of the small size black phosphorus sheet that makes of the embodiment of the present invention 1;
Fig. 3 is the high-resolution-ration transmission electric-lens (HRTEM) of the small size black phosphorus sheet that makes of the embodiment of the present invention 1Figure;
Fig. 4 is the low power transmission electron microscope picture of the small size black phosphorus sheet that makes of the embodiment of the present invention 4;
Fig. 5 is AFM (AFM) figure of the small size black phosphorus sheet that makes of the embodiment of the present invention 4;
Fig. 6 is the size statistical chart carrying out for lines in Fig. 51,2,3;
Fig. 7 is the low power transmission electron microscope picture of the black phosphorus sheet that makes of comparative example 1;
Fig. 8 is the low power transmission electron microscope picture of the black phosphorus sheet that makes of comparative example 2.
Detailed description of the invention
The following stated is the preferred embodiment of the embodiment of the present invention, it should be pointed out that for the artThose of ordinary skill, not departing under the prerequisite of embodiment of the present invention principle, can also make some changingEnter and retouch, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Divide multiple embodiment to be further detailed the embodiment of the present invention below. The embodiment of the present invention is not limitDue to following specific embodiment. In the scope of constant principal right, carrying out that can be suitable changed and implements.
In the embodiment of the present invention, described black phosphorus block is to buy from Smart-Elements company.
The ultrasonic instrument used of described probe-type is that the BILON-1800Y type of Shanghai Bi Lang Instrument Ltd. is superSound wave cell pulverization instrument, the ultrasonic instrument used of described water-bath is that Kunshan Ultrasonic Instruments Co., Ltd. producesKQ-300DE type numerical control supersonic cleaning apparatus.
Embodiment 1
A preparation method for small size black phosphorus sheet, comprises the steps:
Take the black phosphorus block of 25mg at the glove box of inflated with nitrogen, milled and be distributed to the N-of 25mLMethyl pyrrolidone, seals, and obtains the dispersion liquid of 1mg/ml; Ultrasonic under 1200W probe ultrasonic power3 hours, then and then ultrasonic 10 hours of water-bath under 300W power, whole ultrasonic procedure is all to pass through iceBathe and to be controlled at that 277K completes below; Then centrifugal under 7000 revs/min of rotating speeds, centrifugation time is 20Minute, get supernatant liquor, obtain being dispersed in the small size black phosphorus sheet in 1-METHYLPYRROLIDONE.
The present embodiment 1 products therefrom is characterized, and as shown in FIG. 1 to 3, wherein, Fig. 1 is little to resultUltraviolet-visible-near-infrared absorption spectrum the figure of size black phosphorus sheet in 1-METHYLPYRROLIDONE solution; Fig. 2 isThe low power transmission electron microscope picture of small size black phosphorus sheet; Fig. 3 is the high-resolution-ration transmission electric-lens figure of small size black phosphorus sheet.As can be seen from Figure 1: small size black phosphorus sheet reveals obvious absorption characteristic at 300-900nm region list,Its absorption peak is about 485nm, and hour, its band gap increases to some extent relation to the size of this and black phosphorus sheet;Fig. 2 illustrates that the monodispersity of the small size black phosphorus sheet making is good, size homogeneous, and its lateral dimension is at 2.6nmLeft and right; Can significantly see the lattice fringe of black phosphorus thin slice atomic layer from Fig. 3, wherein, spacing of lattice is0.256nm is corresponding to (111) crystal face of black phosphorus crystal.
Embodiment 2
A preparation method for small size black phosphorus sheet, comprises the steps:
Take the black phosphorus block of 15mg at the glove box of inflated with nitrogen, milled and be distributed to the N-first of 25mLBase pyrrolidones, seals, and obtains the dispersion liquid of 0.6mg/ml; Super under 1400W probe-type ultrasonic powerSound 1 hour, then and then ultrasonic 8 hours of water-bath under 400W power, whole ultrasonic procedure is all passed throughIce bath is controlled at that 277K completes below; Then centrifugal under 5000 revs/min of rotating speeds, centrifugation time is20 minutes, get supernatant liquor, obtain small size black phosphorus sheet.
Embodiment 3
A preparation method for small size black phosphorus sheet, comprises the steps:
Take the black phosphorus block of 30mg at the glove box of inflated with nitrogen, milled and be distributed to the diformazan of 25mLIn base sulfoxide, seal, obtain the dispersion liquid of 1.2mg/ml; Under 1000W probe-type ultrasonic power ultrasonic 4Hour, then and then ultrasonic 12 hours of water-bath under 100W power, whole ultrasonic procedure is all to pass through ice bathBe controlled at that 277K completes below; Then centrifugal under 9000 revs/min of rotating speeds, centrifugation time is 10 pointsClock, gets supernatant liquor, obtains small size black phosphorus sheet.
Embodiment 4
A preparation method for small size black phosphorus sheet, comprises the steps:
Under isolated air conditions, take the black phosphorus block of 25mg, milled and be distributed to the nothing of 25mLIn water-ethanol, obtain the dispersion liquid of 1mg/mL, sealing; And then under 1000W probe-type ultrasonic powerUltrasonic 2 hours, then ultrasonic 10 hours of water-bath under 300W power, whole ultrasonic procedure is all to pass through iceTemperature is controlled in bath; Then under 8000 revs/min of rotating speeds centrifugal 20 minutes, get supernatant liquor, surpassedLittle black phosphorus nanometer sheet.
The present embodiment 4 products therefroms are characterized, and result is as shown in Fig. 4～Fig. 5, and wherein, Fig. 4 is thisThe low power transmission electron microscope picture of the small size black phosphorus sheet that inventive embodiments 4 makes; Fig. 5 is the embodiment of the present invention 4AFM (AFM) figure of the small size black phosphorus sheet making.
As seen from Figure 4, the size homogeneous of described small size black phosphorus sheet, good dispersion, its lateral dimension existsAbout 2nm, than the particle diameter that adopts 1-METHYLPYRROLIDONE to make dispersant to stir the small size black phosphorus sheet makingSmaller, this may be by due to its polarity. And the small size black phosphorus sheet making is carried out to AFM(AFM) characterize, result as shown in Fig. 5-6, each line in abscissa in Fig. 6 " position " representative graph 5The length of bar, as can be seen from Figure 5, the radial dimension of described small size black phosphorus sheet is in 0.8-2nm left and right.
Embodiment 5
Under isolated air conditions, take a certain amount of black phosphorus block, milled and be distributed to appropriate absolute ethyl alcoholIn, obtain the dispersion liquid of 1.2mg/mL, sealing; Under 1400W probe-type ultrasonic power ultrasonic 3 hours,Then and then ultrasonic 10 hours of water-bath under 300W power, whole ultrasonic procedure is all to control by ice bathTemperature; Then centrifugal under 9000 revs/min of rotating speeds, centrifugation time is 20 minutes, gets supernatant liquor,To extra small black phosphorus nanometer sheet.
Embodiment 6
A preparation method for small size black phosphorus sheet, comprises the steps:
Under isolated air conditions, take a certain amount of black phosphorus block, milled and be distributed to appropriate anhydrous secondIn alcohol, obtain the dispersion liquid of 0.8mg/mL, sealing; First under 1200W probe-type ultrasonic power ultrasonic 3Hour, then and then ultrasonic 12 hours of water-bath under 200W power, whole ultrasonic procedure is all to pass through ice bathControl temperature; Then under 9000 revs/min of rotating speeds centrifugal 15 minutes, get supernatant liquor, obtain extra smallBlack phosphorus nanometer sheet.
For outstanding technique effect of the present invention, now comparative example 1, contrast are set respectively in fact for embodiment 4Execute example 2.
Comparative example 1
A preparation method for black phosphorus sheet, comprises the steps:
Under isolated air conditions, take the black phosphorus block of 25mg, milled and be distributed to the nothing of 25mLIn water-ethanol, obtain the dispersion liquid of 1mg/mL, sealing; And then under 1000W probe-type ultrasonic powerUltrasonic 2 hours, whole ultrasonic procedure was all controlled temperature by ice bath; Then 8000 revs/min of rotating speedsLower centrifugal 20 minutes, get supernatant liquor, obtain extra small black phosphorus nanometer sheet.
Comparative example 2
A preparation method for black phosphorus sheet, comprises the steps:
Under isolated air conditions, take the black phosphorus block of 25mg, milled and be distributed to the nothing of 25mLIn water-ethanol, obtain the dispersion liquid of 1mg/mL, sealing; And then water-bath ultrasonic 10 under 300W powerHour, whole ultrasonic procedure is all controlled temperature by ice bath; Then centrifugal under 8000 revs/min of rotating speeds20 minutes, get supernatant liquor, obtain extra small black phosphorus nanometer sheet.
Fig. 7, Fig. 8 are respectively the transmission electricity of the black phosphorus sheet that comparative example 1, comparative example 2 prepareMirror figure. As shown in Figure 7, super when the organic solvent that is dispersed with the black phosphorus block after grinding only being carried out to probe-typeWhen sonication, black phosphorus mainly exists with thinner sheet, and size is about 200nm, and this just shows spy onlyPin type is ultrasonic only can effectively destroy the interaction between black phosphorus sheet, but can not realize, it is received to small sizeThe transformation of rice sheet; Corresponding when it is in the time only having the ultrasonic processing of water-bath, as shown in Figure 8, the sample obtainingSize greatly about tens nanometers left and right, this shows that water-bath ultrasonic energy plays the cutting to black phosphorus sheet effectively,Make the effect of its size decreases. In addition, obviously see when only ultrasonic by probe-type or while only adopting water-bath ultrasonic,The agglomeration of products obtained therefrom is more serious, cannot obtain that monodispersity is good, size homogeneous, horizontal chi at allThe very little small size black phosphorus sheet in several nanometers.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all at thisAny amendment of doing within bright spirit and principle, be equal to and replace and improvement etc., all should be included in the present inventionProtection domain within.
Claims (10)
1. a preparation method for small size black phosphorus sheet, is characterized in that, comprises the following steps:
(1) under oxygen free condition, get black phosphorus, the particle diameter of described black phosphorus is 5～50 μ m, and described black phosphorus is dividedBe dispersed in the first organic solvent, obtain dispersion liquid, the concentration of described black phosphorus in described dispersion liquid is 0.6～1.2mg/mL；
(2) be first under 1000～1400W, to carry out probe-type ultrasonic 2～4 hours at power by described dispersion liquid,Then be under 200～400W, to carry out water-bath ultrasonic 8～12 hours at power;
(3) after ultrasonic, centrifugal, collect supernatant, obtain small size black phosphorus sheet.
2. preparation method as claimed in claim 1, is characterized in that, described black phosphorus is by by black phosphorus pieceBody grinds and obtains.
3. preparation method as claimed in claim 1, is characterized in that, described small size black phosphorus sheet laterallySize is at 1～3nm.
4. preparation method as claimed in claim 1, is characterized in that, the ultrasonic power of described probe-type is1000～1150W。
5. preparation method as claimed in claim 1, is characterized in that, the ultrasonic power of described water-bath is100～280W。
6. preparation method as claimed in claim 1, is characterized in that, described the first organic solvent is N-Methyl pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone, oxolane, absolute ethyl alcohol, firstOne or more in alcohol, isopropyl alcohol, chloroform and carrene.
7. preparation method as claimed in claim 6, is characterized in that, described the first organic solvent is anhydrousEthanol.
8. preparation method as claimed in claim 1, is characterized in that, the ultrasonic and described water of described probe-typeBathing ultrasonic is all to complete under condition of ice bath, and the temperature of described ice bath is below 4 DEG C.
9. preparation method as claimed in claim 1, is characterized in that, described centrifugal rotating speed is 5000～9000Rev/min, centrifugation time is 15～25 minutes.
10. a small size black phosphorus sheet, is characterized in that, the lateral dimension of described small size black phosphorus sheet is 1～3Nm, longitudinal size is at 0.8～2nm.
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