CN109248317B - Method for modifying black phosphorus by using azobenzene derivative and obtained compound - Google Patents
Method for modifying black phosphorus by using azobenzene derivative and obtained compound Download PDFInfo
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- CN109248317B CN109248317B CN201811315230.1A CN201811315230A CN109248317B CN 109248317 B CN109248317 B CN 109248317B CN 201811315230 A CN201811315230 A CN 201811315230A CN 109248317 B CN109248317 B CN 109248317B
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Abstract
The invention discloses a method for improving black phosphorus by utilizing azobenzene derivatives, which comprises the steps of adding black phosphorus and azobenzene derivatives into an organic solvent to obtain a mixed solution; and carrying out water bath ultrasound on the mixed solution at the temperature of 0-20 ℃, wherein the ultrasound time is 6-8 hours, the alternating illumination of ultraviolet light and visible light is given in the ultrasound process, the alternating time is 5-30 min, standing is carried out after the ultrasound is finished, the supernatant is taken for centrifugal separation, and the precipitate is collected to obtain the azobenzene derivative and black phosphorus nanosheet compound. The method has low cost and high efficiency. The azobenzene derivative and the solution-dispersed black phosphorus compound prepared by the method have wide application prospects in the fields of solar thermal energy fuel, photothermal therapy and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of functional/composite materials. Relates to a method for modifying black phosphorus by using azobenzene and a compound obtained by the method.
Background
The black phosphorus is a natural semiconductor, the band gap of the black phosphorus is related to the number of layers of the black phosphorus, and the black phosphorus has adjustability, excellent electrical performance and unique anisotropy of mechanics, electricity and heat. In addition, the unique biocompatibility and degradability of the black phosphorus make the black phosphorus an excellent intelligent photoresponse biomedical material. Although black phosphorus has shown great potential in many fields, it has a fatal defect: lack of stability. When contacting water and oxygen, the black phosphor layer is oxidized and deteriorated in a short time. This drawback greatly limits the research and industrial application of black phosphorus. The azobenzene molecule is a typical photoresponsive molecule and is widely applied to preparation of photoresponsive composite materials.
Disclosure of Invention
The invention aims to provide a method for modifying black phosphorus by using azobenzene derivatives and a compound obtained by the method, wherein the compound can be used for preparing energy storage materials and photothermal therapy.
In order to achieve the purpose, the invention provides a method for modifying black phosphorus by using azobenzene derivatives, the azobenzene derivatives selected by the invention are subjected to organic solution liquid phase dispersion to prepare a compound of black phosphorus nanosheets and azobenzene derivatives, wherein the azobenzene derivatives have better thermal stability, carry out isomerization reaction under different illumination conditions, can play a synergistic effect with an organic solvent in an ultrasonic process, and simultaneously effectively improve the dispersion efficiency of the black phosphorus in the ultrasonic process through the isomerization reaction.
The method comprises the following specific steps:
adding black phosphorus and azobenzene derivatives into an organic solvent to obtain a mixed solution; and carrying out water bath ultrasound on the mixed solution at the temperature of 0-20 ℃, wherein the ultrasound time is 6-8 hours, the alternating illumination of ultraviolet light and visible light is given in the ultrasound process, the alternating time is 5-30 min, standing is carried out after the ultrasound is finished, the supernatant is taken for centrifugal separation, and the precipitate is collected to obtain the black phosphorus compound.
Specifically, the mass ratio of the black phosphorus to the azobenzene derivative is 1.5: 0.1-15. For the invention, the product black phosphorus compound is only a layer of azobenzene molecules adsorbed on the surface layer of the black phosphorus nanosheet, so that the azobenzene derivative can be used in excess according to the needs. For the present invention, the ratio is preferably 1.5:1 to 15, more preferably 1: 10.
Specifically, alternating illumination with the wavelength of 365nm and the wavelength of 450nm is given in the ultrasonic process, and the alternating time is 5-30 min. Preferably, the alternating time is 10-15 minutes.
Specifically, the organic solvent is selected from one or more of N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide and water. Dimethyl sulfoxide (abbreviated as DMSO) is preferred.
Specifically, the black phosphorus is a black phosphorus nanosheet, and is obtained by grinding a black phosphorus crystal.
Specifically, the azobenzene derivative is AB-OC4H8-R, wherein R is: quaternary ammonium salts, amino groups, n-hexyl groups, mercapto groups; or AB-OC4H8-S-S-C4H8O-AB。
For example: AB-O-C4H8-NMe3 +I-(derivative 1 for short); AB-OC4H8-NH2(derivative 2 for short); AB-OC4H8-C6H13(derivative 3 for short); AB-OC4H8-SH (derivative 4 for short); azobenzene disulfide AB-OC4H8-S-S-C4H8O-AB (derivative 4D for short). AB-O-C is preferred for the purposes of the present invention4H8-NMe3 +I-Or AB-O-C4H8-SH。
Specifically, the power of the water bath ultrasound is 400-600W.
Specifically, the centrifugal separation conditions are as follows: the rotating speed of the centrifugation is 5000-15000 rpm, and the time of the centrifugation is 10-30 min. Preferably, the rotation speed of the centrifuge is 10000 rpm.
Specifically, the vacuum drying conditions are as follows: the pressure is-0.05 to-0.1 MPa, the temperature is 50 to 70 ℃.
The invention also provides a black phosphorus compound prepared by the method, wherein the black phosphorus compound contains 5-15% of azobenzene derivatives.
Furthermore, the black phosphorus compound is in a nano sheet shape, the transverse size of the nano sheet is 100-500 nm, the thickness of the nano sheet is 10-40 nm, and the black phosphorus compound contains 7-13% of azobenzene derivatives.
For the invention, the mechanism of the azobenzene derivative and the black phosphorus nanosheet compound obtained by dispersing the black phosphorus in DMSO by the azobenzene derivative is as follows: because the surface energy of the solvent is closer to that of the black phosphorus nanosheet, under the ultrasonic action, the solvent enters the black phosphorus nanosheet layer, further azobenzene derivatives enter the black phosphorus nanosheet layer, weak interaction between the layers is destroyed, under the illumination condition, azobenzene molecules entering the layers generate cis-trans isomerization reaction, the black phosphorus is further spread, massive black phosphorus is dispersed in the solution, the dispersed flaky black phosphorus is in a metastable state in the solvent, and the dispersed black phosphorus nanosheet can stably exist through electrostatic interaction or Van der Waals interaction by the azobenzene derivatives adsorbed on the surface, so that secondary agglomeration or secondary accumulation is effectively prevented, and the black phosphorus nanosheet is stabilized, and finally the compound of the azobenzene derivatives and the black phosphorus is obtained.
Has the advantages that: according to the preparation method of the azobenzene derivative and the solution dispersion black phosphorus nanosheet, provided by the invention, the azobenzene derivative is added, illumination with different wavelengths is applied in the ultrasonic process, and the stable azobenzene derivative and the solution dispersion black phosphorus compound are obtained while the black phosphorus dispersion efficiency is improved through the cis-trans isomerization reaction of the azobenzene derivative. The method has low cost and high efficiency. The azobenzene derivative and the solution-dispersed black phosphorus compound prepared by the method have wide application prospects in the fields of solar thermal energy fuel, photothermal therapy and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a black phosphorus, black phosphorus composite, dispersed in a solution.
FIG. 2 is an atomic force microscope image of black phosphorus dispersed with and without the addition of an azo derivative and a comparison of the heights thereof.
FIG. 3 is a transmission electron micrograph of the black phosphorus, black phosphorus composite dispersed in the solution.
FIG. 4 is a graph comparing Zeta potential values of black phosphorus dispersed in solution and black phosphorus composite.
Detailed Description
In order to make the technical solutions better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, but not all embodiments.
A method for dispersing black phosphorus nanosheets by azobenzene derivatives is to grind blocky black phosphorus crystals into black phosphorus with smaller size and uniformly mix the black phosphorus and the azobenzene derivatives in an organic solvent. Argon gas was introduced into the solution for 10 minutes, and then the solution was sealed with a sealing film. And (3) ultrasonically dispersing under a water bath condition, applying unequal intermittent ultraviolet and visible light for 5-30 minutes in the dispersing process, and switching the azobenzene derivative between a trans-form configuration and a cis-form configuration to achieve the aim of assisting in dispersing the blocky black phosphorus. And (3) carrying out ultrasonic treatment for 6-8 hours, standing after the ultrasonic treatment is finished, and finally centrifuging, carrying out vacuum filtration and drying to obtain a target product.
The preparation steps of the invention are as follows.
Mixing the black phosphorus and the azobenzene derivative into the organic solvent according to the mass ratio of 1.5: 0.1-15, wherein the preferred mass ratio is 1: 10. The concentration of azobenzene derivative in the mixed solution is controlled to be 0.0001-0.1mmol/L, the solvent is one or a mixture of more than two of N-methyl pyrrolidone, dimethyl sulfoxide, N-dimethylformamide and water, and the azobenzene derivative is one or a mixture of more than two of para-substituted long alkyl chain molecules with different terminal groups (amino, sulfydryl, N-hexyl and quaternary ammonium salt).
And (3) isolating the mixed solution from air, and carrying out a liquid phase ultrasonic dispersion experiment at a certain temperature, wherein the temperature in the liquid phase dispersion process is controlled to be 0-20 degrees, and the ultrasonic time is 6-8 hours.
And centrifuging the product obtained by ultrasonic dispersion, and drying to obtain the target product. The centrifugal speed is 10000-15000 rpm, and the vacuum drying temperature is 50-70 degrees.
The mass content of the azobenzene derivative in the black phosphorus compound is 7-13% through calculation according to the transverse size of the black phosphorus nanosheet and an adsorption model.
Example 1
Putting the black phosphorus nanosheet into dimethyl sulfoxide (DMSO), controlling the temperature to be 0-20 ℃ in the water bath ultrasonic process, carrying out ultrasonic treatment for 8 hours, standing the solution for a period of time after the ultrasonic treatment is finished, and finally centrifuging the ultrasonic mixed solution for 30min at the rotation speed of 10000 rpm; the obtained supernatant is the solution of the black phosphorus nanosheet and azobenzene derivative compound; the bottom precipitate was dried in vacuum at 60 ℃ to give the desired product.
Example 2
Putting the black phosphorus nanosheet and azobenzene derivative molecules into dimethyl sulfoxide (DMSO) according to the mass ratio of 1:10, wherein the azobenzene molecules are AB-O-C4H8-NMe3 +I-The concentration is controlled to be 0.01 mg/mL; controlling the temperature of liquid-phase ultrasonic dispersion to be 0-20 degrees; the ultrasonic time is 8 h; centrifuging the mixed solution after ultrasonic treatment for 30min at the rotating speed of 10000 rpm; the obtained supernatant is the solution of the black phosphorus nanosheet and azobenzene derivative compound; the bottom precipitate was dried in vacuum at 60 ℃ to give the desired product.
Example 3
The basic procedure was substantially the same as in example 2. With the difference that azobenzene derivatives AB-OC with amino group as end group are used4H8-NH2。
Example 4
The basic procedure was substantially the same as in example 2. With the difference that azobenzene derivatives AB-OC with n-hexyl end group are used4H8-C6H13。
Example 5
The basic procedure was substantially the same as in example 2. With the difference that azobenzene derivatives AB-OC with mercapto group as end group are used4H8-SH。
Example 6
The basic procedure was substantially the same as in example 2. With the difference that azobenzene disulphide AB-OC is used4H8-S-S-C4H8O-AB。
FIG. 1 is a scanning electron microscope image of a black phosphorus nanosheet dispersed in a solution (comparison of example 1 and example 2), and it can be seen that the transverse dimension of the obtained product is 100-500 nm.
Fig. 2 is an atomic force microscope image of black phosphorus dispersed with and without an azo benzene derivative added and a graphical representation of the height thereof (comparison of example 1 and example 2), and it can be seen from fig. 2 that the dispersed black phosphorus nanosheets have a larger lateral dimension and a thinner thickness after the addition of the azo benzene derivative.
FIG. 3 is a transmission electron microscope image of the black phosphorus nanosheets dispersed in the solution of examples 1-6, from which it can be seen that the exfoliated black phosphorus nanosheets have a larger size.
FIG. 4 is a measured value of Zeta potential of the aqueous solution in examples 1-6, and it can be seen from the figure that the Zeta potential of the black phosphorus nanosheet modified by the azobenzene derivative is obviously higher than that of the unmodified black phosphorus nanosheet.
Table 1 comparison of the results of different azobenzene derivative molecular pairs on the dispersion of black phosphorus in DMSO solution
Note: in the table, the black phosphorus content in the solution is: absorbance value of ultraviolet visible absorption spectrum at 400 nm.
Table 1 shows the black phosphorus dispersing efficiency in different solvents, and the absorbance value of the ultraviolet absorption spectrum at 400nm of each sample is taken as a discrimination standard after the sample is centrifuged at 10000rpm for 30 minutes under the same experimental conditions. We can see that the absorbance is the greatest in DMSO solvent, and therefore we believe that the effect of dispersing black phosphorus in DMSO solvent is the best. DMSO solvents were used in the examples that follow. In examples 1-6, we compared the effect of different azobenzene derivative molecules on the dispersion of black phosphorus, where AB-O-C4H8-NMe3 +I-And AB-O-C4H8The effect of dispersing the-SH molecules is the best.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (5)
1. A method for modifying black phosphorus by using azobenzene derivatives is characterized by comprising the following steps: adding black phosphorus and azobenzene derivatives into an organic solvent to obtain a mixed solution; carrying out water bath ultrasound on the mixed solution at the temperature of 0-20 ℃, wherein the ultrasound time is 6-8 hours, giving alternating illumination of ultraviolet light and visible light in the ultrasound process, the alternating time is 5-30 min, standing after the ultrasound is finished, taking supernate, carrying out centrifugal separation, collecting precipitate, and carrying out vacuum drying to obtain a black phosphorus compound;
the azobenzene derivative is AB-OC4H8-S-S-C4H8O-AB; or AB-OC4H8-R, wherein R is: quaternary ammonium salt and mercapto group;
giving alternate illumination with the wavelength of 365nm and 450nm respectively in the ultrasonic process, wherein the alternate time is 5-30 min;
the power of the water bath ultrasound is 400-600W;
the vacuum drying conditions are as follows: the pressure is-0.05 to-0.1 MPa, and the temperature is 50 to 70 ℃;
the organic solvent is dimethyl sulfoxide.
2. The method for modifying black phosphorus by using azobenzene derivatives as claimed in claim 1, wherein the mass ratio of black phosphorus to azobenzene derivatives is 1.5: 0.1-10.
3. The method for modifying black phosphorus by using azobenzene derivative as claimed in claim 1, wherein the centrifugal separation condition is as follows: the rotating speed of the centrifugation is 5000-15000 rpm, and the time of the centrifugation is 10-30 min.
4. A black phosphorus composite obtained by the method according to any one of claims 1 to 3.
5. The black phosphorus composite according to claim 4, wherein the azobenzene derivative is contained in an amount of 7 to 13%.
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Citations (4)
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|---|---|---|---|---|
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| WO2016018988A1 (en) * | 2014-07-31 | 2016-02-04 | The University Of North Carolina At Chapel Hill | Two dimensional materials produced by the liquid exfoliation of black phosphorus |
| CN106267201A (en) * | 2016-08-26 | 2017-01-04 | 深圳先进技术研究院 | A kind of black phosphorus of polymer wrapped and preparation method and application |
| CN107469082A (en) * | 2017-08-21 | 2017-12-15 | 中南大学 | A kind of application of black phosphorus nanometer sheet |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016018988A1 (en) * | 2014-07-31 | 2016-02-04 | The University Of North Carolina At Chapel Hill | Two dimensional materials produced by the liquid exfoliation of black phosphorus |
| CN104961113A (en) * | 2015-07-01 | 2015-10-07 | 北京石油化工学院 | Method for preparing phosphaalkene |
| CN106267201A (en) * | 2016-08-26 | 2017-01-04 | 深圳先进技术研究院 | A kind of black phosphorus of polymer wrapped and preparation method and application |
| CN107469082A (en) * | 2017-08-21 | 2017-12-15 | 中南大学 | A kind of application of black phosphorus nanometer sheet |
Non-Patent Citations (2)
| Title |
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| Light-enhanced liquid-phase exfoliation and current photoswitching in grapheme-azobenzene composites;Markus Dobbelin, et al.;《Nature Communications》;20160407;第7卷;第1-9页 * |
| 超薄二维黑磷材料的制备及其光学性质研究;徐靖银;《中国优秀硕士学位论文全文数据库工程科技I辑》;20160815(第08期);第B015-122页 * |
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