CN110078034B - Preparation method of organic metal framework-coated two-dimensional black phosphorus nanosheet - Google Patents
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Abstract
A preparation method of organic metal framework coated two-dimensional black phosphorus nanosheets relates to black phosphorus nanosheets. Preparing a two-dimensional black phosphorus nanosheet; preparing a metal ion modified black phosphorus nanosheet; mixing and dispersing the black phosphorus nanosheet modified by the metal ions and the organic ligand in N, N-dimethylformamide DMF, and transferring the mixed solution into a reaction kettle for constant-temperature crystallization; and cooling the reaction kettle to room temperature, centrifuging and washing to obtain the organic metal framework-coated two-dimensional black phosphorus nanosheet. The metal ions are fixed on the surface of the black phosphorus by the method of forming the metal organic framework on the surface of the black phosphorus, the electron cloud density of the surface of the black phosphorus is reduced by the metal ions, the contact between the metal ions and water and oxygen is reduced by the MOF coating, and the stability of the black phosphorus is improved. Due to the high porosity of the organic metal framework, the prepared organic metal framework is coated with black phosphorus and can be applied to gas detection or gas storage.
Description
Technical Field
The invention relates to a black phosphorus nanosheet, in particular to a preparation method of an organic metal framework-coated two-dimensional black phosphorus nanosheet.
Background
The black phosphorus belongs to one of allotropes of phosphorus, is prepared by American scientists as early as 1914, and has extremely harsh synthesis conditions. Compared with the common black phosphorus and white phosphorus, the thermodynamic stability of the block black phosphorus is relatively better. The report of the literature suggests that the black phosphorus nanosheet can be obtained by using a mechanical stripping method, and the significant characteristic of the black phosphorus nanosheet is that the band gap can be adjusted through the number of layers, and the variation range is 0.3-2.0 eV, which just makes up for the defect of the graphene band gap. The black phosphorus nanosheet has the other characteristic of biocompatibility, the phosphorus element is an essential element for life movement, and the black phosphorus can be naturally degraded into phosphate under physiological conditions. The unique crystal system structure, in-plane anisotropy and biocompatibility of the black phosphorus enable the black phosphorus to have wide application in the fields of electronic devices and biology.
Compared with other two-dimensional materials, black phosphorus has poor stability in an environment containing water and oxygen, and is easy to react with water and oxygen to generate various oxides of phosphorus, so that the structure is damaged, and the physical and chemical properties of the black phosphorus are affected, so that how to stabilize the black phosphorus is an important part in the development of black phosphorus materials.
At present, researchers mainly reduce the contact of black phosphorus with oxygen and water by using physical or chemical methods, but these methods have more or less defects. For example, the method for chemically modifying the ligand of titanium or the diazobenzene derivative on black phosphorus is too complex (Angew. chem. int. Ed.,2016,55, 5003-5007; Natchem.2016,8,597-602.) and harsh to the experimental conditions; in addition, the use of polymer encapsulation such as PLGA (Nat commun.,2016,7,12967) has the problem of destroying the two-dimensional structure of black phosphorus.
Metal Organic Frameworks (MOFs) have gained popularity as a new porous material in the last 60 th century. In 1999, U.S. scientist o.M. yaghi reported in Nature the synthesis of MOF-5 with three-dimensional network structure and the study of hydrogen storage property thereof, the pore size and specific surface area of which are far larger than those of the traditional molecular sieve, so that the materials are widely concerned by researchers, and the development of MOFs research is started. In the next decades, MOFs materials have rapidly become hot spots for research in the fields of materials, chemistry and physics. The most important structural characteristics of the MOFs are that the MOFs have ultrahigh porosity (more than 90 percent of porosity) and ultrahigh internal surface area (up to 10000 m) 2 /g) and super-high specific surface area, and the characteristics of Lewis acid and Lewis base and the like of the MOFs, so that the MOFs material is widely applied to the fields of gas storage, gas separation, biosensors, catalysis, drug release and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an organic metal framework-coated two-dimensional black phosphorus nanosheet, which can improve the stability of black phosphorus in a common environment on the premise of not damaging a two-dimensional structure of the black phosphorus.
The invention comprises the following steps:
1) preparing a two-dimensional black phosphorus nanosheet;
2) preparing a metal ion modified black phosphorus nanosheet;
3) mixing and dispersing the black phosphorus nanosheet modified by the metal ions and the organic ligand in N, N-dimethylformamide DMF, and transferring the mixed solution into a reaction kettle for constant-temperature crystallization;
4) and cooling the reaction kettle to room temperature, centrifuging and washing to obtain the organic metal framework-coated two-dimensional black phosphorus nanosheet.
In step 1), the specific method for preparing the two-dimensional black phosphorus nanosheet may be: stripping black phosphorus by using an ultrasonic-assisted liquid phase, grinding and crushing the black phosphorus, dispersing the ground black phosphorus in a PVP solution, and performing ultrasonic treatment by using a probe; the mass concentration of the PVP solution can be 0.1 mg/mL; the time of the probe ultrasonic treatment can be 5-10 h.
In step 2), the specific method for preparing the metal ion modified black phosphorus nanosheet may be: dispersing metal salt in anhydrous ethanol, wherein the metal ion species includes but is not limited to Cu 2+ ，Zn 2+ ，Ni + ，Co 2+ ，Mn 2+ ，Fe 3+ ，Sn 4+ ，Ca 2+ ，Al 3+ ，Ti 4+ ，Cr 3+ Etc., the molar concentration of the metal salt may be 8 to 16 mmol/L.
In step 3), the organic ligand includes but is not limited to one of terephthalic acid, aminated terephthalic acid, dimethyl imidazole, terephthalic acid, etc.; the temperature of the constant temperature crystallization can be 135-200 ℃, and the time of the constant temperature crystallization can be varied from several hours to several days.
In the step 4), the centrifugal washing method is to use ethanol or methanol for washing for multiple times, and the centrifugal speed can be 6000 to 8000 r/min.
The invention has the following outstanding advantages:
1) according to the black phosphorus coated by the organic metal framework, the metal ions are fixed on the surface of the black phosphorus by the method of forming the metal organic framework on the surface of the black phosphorus, the electron cloud density of the surface of the black phosphorus is reduced by the metal ions, the contact between the metal ions and water and oxygen is reduced by the coating of the MOF, and the stability of the black phosphorus is improved.
2) Due to the high porosity of the organic metal framework, the prepared organic metal framework is coated with black phosphorus and can be applied to gas detection or gas storage.
Drawings
FIG. 1 shows black phosphorus and organic metal framework NH 2 MIL-53(Al) and organometallic framework NH 2 -X-ray diffraction pattern of MIL-53(Al) coated black phosphorus.
FIG. 2 shows an organometallic framework NH 2 Transmission electron micrograph of MIL-53(Al) coated black phosphor.
FIG. 3 shows black phosphorus and organic metal framework NH 2 Uv absorption spectrum over time of MIL-53(Al) coated black phosphorus. In FIG. 3, a is black phosphorus, and b is an organometallic framework NH 2 MIL-53(Al) coated black phosphorus.
FIG. 4 is a transmission electron microscope image of black phosphor coated by an organic metal framework MIL-53 (Fe).
FIG. 5 is an X-ray diffraction pattern of black phosphorus, organo-metallic framework ZIF-8 and organo-metallic framework ZIF-8 coated black phosphorus.
FIG. 6 is a transmission electron microscope image of the organic metal framework ZIF-8 coated black phosphor.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described in the following embodiments.
Example 1
This example provides an organometallic framework NH 2 -MIL-53(Al) black phosphorus coating process comprising the steps of:
(1) weighing 60mg of black phosphorus in an oxygen-free environment, and grinding in 0.1mg/mL PVP aqueous solution; performing ultrasonic treatment for 5 hours in a low-temperature water bath by using a 950W probe; centrifuging the dispersion liquid at 4000rpm for 10min, taking supernatant, centrifuging the supernatant at 12000rpm for 6min, taking precipitate, dispersing the precipitate in absolute ethyl alcohol, and repeating the centrifuging step to obtain the two-dimensional black phosphorus nanosheet (marked as BP).
(2) Weighing a certain amount of anhydrous aluminum chloride, and dissolving the anhydrous aluminum chloride in anhydrous ethanol, wherein the concentration of the anhydrous aluminum chloride is 8 mmol/L; and (2) re-dispersing the two-dimensional black phosphorus nanosheets obtained in the step (1) in an ethanol solution of aluminum chloride, and then stirring overnight.
(3) The dispersion from step (2) was dried under vacuum and redispersed in 15ml of N-dimethylformamide DMF, 100mg of aminated terephthalic acid was added and stirred for 5 hours.
(4) And transferring the solution into a 45mL reaction kettle, heating the solution in an oven at the constant temperature of 135 ℃ for 5h, cooling the solution to room temperature, centrifuging the solution at the rotating speed of 8000rpm, and washing the solution for 3 times to obtain a product (marked as BP @ MIL-53 (Al)).
Respectively dispersing the prepared BP and BP @ MIL-53(Al) in water100. mu.L of each was dropped on a glass slide, dried in vacuo, and analyzed by X-ray diffraction spectroscopy, and the results are shown in FIG. 1. As can be seen from FIG. 1, NH 2 The black phosphorus coated by MIL-53(Al) has characteristic peaks of the black phosphorus and NH 2 Characteristic peak of MIL-53(Al), the results indicate that the organometallic framework has been successfully coated with two-dimensional black phosphorus nanoplates.
Respectively dispersing the prepared BP and BP @ MIL-53(Al) in water, dropwise adding the mixture to a micro-grid copper mesh, drying in vacuum, and observing the structure of the micro-grid copper mesh by using a transmission electron microscope, wherein the result is shown in figure 2, and the surface of the black phosphorus is uniformly coated with a thin layer of NH 2 MIL-53(Al), which roughens black phosphorus with a smooth surface, so that the organic metal framework can be successfully coated.
The prepared BP and BP @ MIL-53(Al) are respectively dispersed in PBS buffer solution, respectively placed for a period of time, and an ultraviolet absorption spectrum of the solution is tested by using an ultraviolet spectrophotometer, and the result is shown in figure 3. As shown in fig. 3, the absorption of black phosphorus rapidly decreased over a period of 9 days, indicating that black phosphorus is rapidly degraded in PBS solution, while BP @ MIL-53(Al) shows a slight decrease in uv spectrum even after 30 days, demonstrating that the encapsulation of the organometallic framework enables BP to maintain good stability in PBS solution.
Example 2
The embodiment provides a method for coating black phosphorus by an organic metal framework MIL-53(Fe), which comprises the following steps:
(1) weighing 60mg of black phosphorus in an oxygen-free environment, and grinding in 0.1mg/mL PVP aqueous solution; performing ultrasonic treatment for 5h in a low-temperature water bath by using a 950W probe; centrifuging the dispersion liquid at 4000rpm for 10min, taking supernatant, centrifuging the supernatant at 12000rpm for 6min, taking precipitate, dispersing the precipitate in absolute ethyl alcohol, and repeating the centrifuging step to obtain the two-dimensional black phosphorus nanosheet (marked as BP).
(2) Weighing a certain amount of anhydrous zinc chloride, and dissolving the anhydrous zinc chloride in anhydrous ethanol, wherein the concentration is 8 mmol/L; and (2) re-dispersing the two-dimensional black phosphorus nanosheets obtained in the step (1) in an ethanol solution of zinc chloride, and then stirring overnight.
(3) The dispersion from step (2) was dried under vacuum and redispersed in 15ml of N-dimethylformamide DMF, 100mg of terephthalic acid was added and stirred for 5 hours.
(4) And transferring the solution into a 45mL reaction kettle, heating the solution in an oven at the constant temperature of 135 ℃ for 15h, cooling the solution to room temperature, centrifuging the solution at the rotating speed of 8000rpm, and washing the solution for 3 times to obtain a product (marked as BP @ MIL-53 (Fe)).
The prepared BP and BP @ MIL-53(Fe) are respectively dispersed in water, and are dripped on a micro-grid copper mesh, after vacuum drying, the structure observation is carried out by using a transmission electron microscope, and the result is shown in figure 4, the surface of the black phosphorus is uniformly coated with a thin layer of BP @ MIL-53(Fe), and the surface of the black phosphorus is roughened by the coating of the MIL-53(Fe), so that the successful coating of the organic metal framework is proved.
Example 3
The embodiment provides a method for coating black phosphorus by an organic metal framework ZIF-8, which comprises the following steps:
(1) weighing 60mg of black phosphorus in an oxygen-free environment, and grinding in 0.1mg/mL PVP aqueous solution; performing ultrasonic treatment for 5h in a low-temperature water bath by using a 950W probe; centrifuging the dispersion liquid at 4000rpm for 10min, taking supernatant, centrifuging the supernatant at 12000rpm for 6min, taking precipitate, dispersing the precipitate in absolute ethyl alcohol, and repeating the centrifuging step to obtain the two-dimensional black phosphorus nanosheet (marked as BP).
(2) Weighing a certain amount of anhydrous zinc chloride, and dissolving the anhydrous zinc chloride in anhydrous ethanol, wherein the concentration is 8 mmol/L; and (2) re-dispersing the two-dimensional black phosphorus nanosheets obtained in the step (1) in an ethanol solution of zinc chloride, and then stirring overnight.
(3) The dispersion from step (2) was dried under vacuum and redispersed in 15ml of N-dimethylformamide DMF, 100mg of dimethylimidazole was added and stirred for 5 h.
(4) And transferring the solution into a 45mL reaction kettle, heating the solution in an oven at the constant temperature of 135 ℃ for 10h, cooling the solution to room temperature, centrifuging the solution at the rotating speed of 8000rpm, and washing the solution for 3 times to obtain a product (marked as BP @ ZIF-8).
The prepared BP and BP @ ZIF-8 were dispersed in water, 100. mu.L of each was dropped on a glass plate, vacuum-dried, and analyzed by X-ray diffraction spectroscopy, and the results are shown in FIG. 1. As can be seen from FIG. 5, the black phosphorus coated with ZIF-8 shows a characteristic peak of the black phosphorus and a characteristic peak of the ZIF-8, and the results show that the organic metal framework has been successfully coated with two-dimensional black phosphorus nanosheets.
And respectively dispersing the prepared BP and BP @ ZIF-8 in water, dropwise adding the mixture to a micro-grid copper net, carrying out vacuum drying, and carrying out structural observation on the mixture by using a transmission electron microscope, wherein the result is shown in figure 6, the surface of the black phosphorus is uniformly coated with a thin ZIF-8 layer, and the successful coating of the organic metal framework is successfully proved.
According to the invention, metal ions are firstly modified on the surface of the black phosphorus, and then an organic ligand is coordinated to grow a uniform organic metal framework layer on the surface in situ, so that the contact between the black phosphorus and water and oxygen is reduced, and the stability of the black phosphorus is improved; on the other hand, the organic metal framework has high surface area and porosity, and is expected to expand the application of the black phosphorus in the fields of gas detection and gas storage. The method for coating the black phosphorus by the organic metal framework has the advantages of simple process and wide application range, and has good applicability to the organic metal frameworks corresponding to various metal ions.
Claims (6)
1. A preparation method of an organic metal framework coated two-dimensional black phosphorus nanosheet is characterized by comprising the following steps:
1) preparing a two-dimensional black phosphorus nanosheet: stripping black phosphorus by using an ultrasonic-assisted liquid phase, grinding and crushing the black phosphorus, dispersing the ground black phosphorus in a PVP solution, and performing ultrasonic treatment by using a probe;
2) preparing a metal ion modified black phosphorus nanosheet: dispersing metal salt in anhydrous ethanol, wherein the metal ion species contains Cu 2+ 、Zn 2+ 、Ni + 、Co 2+ 、Mn 2+ 、Fe 3+ 、Sn 4+ 、Ca 2+ 、Al 3+ 、Ti 4+ 、Cr 3+ One of (1);
3) mixing and dispersing the black phosphorus nanosheet modified by the metal ions and the organic ligand in N, N-dimethylformamide DMF, and transferring the mixed solution into a reaction kettle for constant-temperature crystallization; the organic ligand comprises one of terephthalic acid, aminated terephthalic acid, dimethyl imidazole and terephthalic acid;
4) and cooling the reaction kettle to room temperature, centrifuging and washing to obtain the organic metal framework-coated two-dimensional black phosphorus nanosheet.
2. The method for preparing organic metal framework-coated two-dimensional black phosphorus nanosheets of claim 1, wherein in step 1), the PVP solution has a mass concentration of 0.1 mg/mL.
3. The preparation method of the organic metal framework-coated two-dimensional black phosphorus nanosheet according to claim 1, wherein in step 1), the probe is subjected to ultrasound for 5-10 h.
4. The method for preparing organic metal framework-coated two-dimensional black phosphorus nanosheets of claim 1, wherein in step 2), the molar concentration of the metal salt is 8-16 mmol/L.
5. The preparation method of the organic metal framework-coated two-dimensional black phosphorus nanosheet as claimed in claim 1, wherein in step 3), the temperature of the constant-temperature crystallization is 135-200 ℃, and the time of the constant-temperature crystallization varies from several hours to several days.
6. The method for preparing organic metal framework-coated two-dimensional black phosphorus nanosheets of claim 1, wherein in step 4), the washing by centrifugation is performed multiple times by using ethanol or methanol, and the centrifugation speed is 6000 to 8000 r/min.
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| CN112421038A (en) * | 2020-11-06 | 2021-02-26 | 清华大学 | Composite material of black phosphorus nanosheet coated with metal organic framework and preparation method and application thereof |
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