CN111072041A - Method for rapidly preparing two-dimensional boron alkene - Google Patents
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Abstract
The invention provides a method for rapidly preparing two-dimensional borolene, which comprises a metal boride preparation process, a strong acid type high polymer pretreatment process, an ion exchange process and an irradiation decomposition process, and specifically comprises the following steps: s1, packaging the magnesium alloy and the boron powder in pyrophyllite, processing by using a cubic hydraulic press, and sintering at high pressure to obtain metal boride; s2, washing the strong acid type high polymer with deionized water for 5h, soaking the polymer in dilute sulfuric acid for 5h, washing the polymer to be neutral, and drying the polymer at room temperature for later use; s3, mixing the metal boride and the strong acid type high polymer, placing the mixture into a conical flask, simultaneously adding a polar organic solvent and an inorganic salt for reaction, stirring at room temperature for reaction for 12-48h to obtain boron hydride powder; and S4, decomposing the boron hydride powder by electron beam irradiation to release hydrogen, and drying to obtain the boron alkene nanosheet. Compared with the existing preparation technology of the borane, the method has the advantages of simple operation and low production cost, and can also realize large-scale preparation.
Description
Technical Field
The invention relates to the technical field of two-dimensional nano materials, in particular to a method for quickly preparing two-dimensional boron alkene.
Background
Graphene (Graphene) is a polymer made of carbon atomsIn sp2The two-dimensional carbon nano material with hexagonal honeycomb lattices formed by the hybrid tracks has excellent optical, electrical and mechanical properties and has important application prospects in the fields of photonic sensors, energy sources, biomedicine and the like. Following graphene, two-dimensional materials have attracted great research interest to scientists in many fields due to their unique characteristics of geometry, mechanics, and photoelectricity.
Elemental boron is a primary target because it is a "close neighbor" of carbon. Boron alkene has sp2 hybridized orbit similar to carbon, and the multicenter characteristic of boron-boron bond enables the boron-boron alkene to easily form a vacancy structure on a plane structure, has anisotropy and metallicity, and simultaneously shows unique mechanical, optical and electrical properties, thereby providing unprecedented diversity for the field of two-dimensional materials in the aspects of electronic application, material synthesis and complex structure construction.
In early experimental exploration, boron is easy to be polluted, raw materials are pure, and compatibility of a matrix is mainly faced in the synthesis of the borane. In 2015, the project groups of Guisinger, Hersam and Oganov, etc. successfully grow monoatomic layer boroalkene on the surface of Ag by using the method of high vacuum molecular beam epitaxy technology [ A.J. Mannix, et al, Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs [ J ] Science 2015,150(6267): 1513-. At present, equipment for preparing the boron alkene is high in price, the requirement on preparation conditions is strict, the chemical process is complex, the production cost is high, and the large-scale preparation of the boron alkene and the practical application of the boron alkene are still difficult. Therefore, the invention provides a novel preparation method of the borane.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for rapidly preparing two-dimensional boron alkene, which mainly aims to solve the problems of complex preparation technology, harsh experimental conditions, low purity of target products and high production cost in the prior art, so that the large-batch production can be realized.
The invention provides a method for rapidly preparing two-dimensional borolene, which comprises a metal boride preparation process, a strong acid type high polymer pretreatment process, an ion exchange process and an irradiation decomposition process, and specifically comprises the following steps:
s1, preparing the metal boride to be treated: firstly, encapsulating a mixture of magnesium alloy and boron powder in pyrophyllite according to a mass ratio of 1:2, and placing a sample at a hammer head of a cubic hydraulic press; setting the pressure of the cubic hydraulic press, enabling a hammer of the cubic hydraulic press to compact pyrophyllite, directly pressurizing to 6GPa, gradually increasing the temperature of the cubic hydraulic press, wherein the temperature changes by 30-40 ℃ every time, and the temperature changes for 15min every time until the temperature of the cubic hydraulic press reaches 800 ℃; after reaching the preset test environment, the mixture of the magnesium alloy and the boron powder is sintered for 10-30min under the environment of 6GPa and 800 ℃, the heating is stopped, the mixture is cooled for 30min in a cubic hydraulic press, the pressure is relieved, and the final test product is taken out, so that the metal boride to be treated is obtained.
S2, pretreatment of a strong acid type high polymer: firstly, controlling the room temperature at 20 ℃, putting a strong acid type high molecular polymer into deionized water prepared before an experiment for water washing, and soaking for 5 hours; then, the strong acid type high molecular polymer soaked by deionized water is put into dilute sulfuric acid diluted into 2-5% by volume by concentrated sulfuric acid and soaked for 5 hours; and then taking out the strong acid type high molecular polymer from the dilute sulfuric acid, then putting the high molecular polymer into deionized water for washing until the strong acid type high molecular polymer is detected to be neutral by a pH meter, and finally taking out the strong acid type high molecular polymer, and putting the high molecular polymer at room temperature for air drying for later experiments.
S3, ion exchange: firstly, mixing metal boride and a strong acid type high polymer at the room temperature of 20 ℃ according to the mass ratio of 1:1-10, and placing the mixture into a conical flask filled with magnetons; then adding 200mL of polar organic solvent and 10mg of inorganic salt solid into the conical flask, wherein the inorganic salt solid is mainly used for promoting the release of hydrogen ions; then, stirring the solution by using a magnetic stirrer at room temperature to enable the mixed solution to react for about 12-48 h; then, filtering unreacted metal boride and high molecular polymer by using a vacuum filtration device, and retaining the borohydride solution after reaction; then, carrying out vacuum treatment on the borohydride solution by using a vacuum pump carried by a rotary evaporator, and pumping the polar organic solvent out of the borohydride solution when the set pressure value is-0.1 MPa, so as to only leave borohydride powder; and finally, drying the borohydride powder in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain borohydride.
S4, electron beam irradiation decomposition: first pass N2Then using electron beam energy emitters at N2And (3) under the atmosphere, irradiating the borohydride powder for a certain time by 5-20kV electron beams to obtain the final boron alkene nanosheet.
Preferably, in step S1, the magnesium alloy is a magnesium-lithium alloy, a magnesium-sodium alloy or a magnesium-potassium alloy, so as to increase the activity of magnesium and increase the active sites.
In step S2, the strong acid type high polymer is preferably polyvinylbenzenesulfonic acid or a sulfonic styrene-divinylbenzene copolymer as a carrier for ion exchange.
It may be preferable that the polar organic solution is acetonitrile, methanol or ethanol in step S3 to control the hydrogen ion release rate.
It is preferable that the inorganic salt is sodium chloride, magnesium chloride, potassium chloride or calcium chloride in step S3 to accelerate the hydrogen ion release rate.
It is preferable that the electron beam irradiation time period is 30 to 60min in step S4.
Preferably, the chemical equation involved in step S1 is:
the chemical equation involved in step S2 is:
(MgLi)xB2+2H+→2HB+Mg2+
the chemical equation involved in step S3 is:
compared with the prior art, the invention has the following advantages:
(1) compared with the prior art, the preparation method of the boron alkene has the advantages of simple forming process, low preparation cost, simple operation, safety, reliability and suitability for large-scale preparation of the boron alkene.
(2) According to the invention, the magnesium alloy and the boron powder are compounded at high pressure and high temperature to prepare the metal boride, so that the activity of magnesium is improved, active sites are increased, and the reaction is facilitated; simultaneously, acid washing and activating the strong acid type high molecular polymer to provide a hydrogen ion exchange carrier for the reaction; controlling the release rate of hydrogen ions by using a polar organic solvent, and adding inorganic salt to promote the release of the hydrogen ions; decomposing the sample by electron beam irradiation to obtain the target product.
(3) The obtained product has high purity, less impurities, high quality, batch production and high popularization value.
Drawings
FIG. 1 is an XRD diagram of a boron hydride compound in the method for rapidly preparing two-dimensional borane according to the present invention; and
FIG. 2 is an SEM image of a boron alkene nanosheet in the rapid preparation method of two-dimensional boron alkene.
Detailed Description
The following detailed description is provided to provide a thorough understanding of the technical content, objectives and effects of the present invention.
Aiming at the problems of complex preparation method, high production cost and low yield of the boroxine in the prior art, the invention prepares metal boride by sintering magnesium alloy and boron powder under high pressure, synthesizes boron hydride by proton exchange of the metal boride and strong acid type high molecular polymer, and finally prepares the boroxine nano-sheets by the boron hydride through an electron beam irradiation decomposition process.
The method for rapidly preparing the two-dimensional boron alkene specifically comprises the following steps:
s1, preparing the metal boride to be treated, wherein the chemical formula is
Firstly, encapsulating a mixture of magnesium alloy and boron powder in pyrophyllite according to a mass ratio of 1:2, and placing a well-mixed sample at a hammer head of a cubic hydraulic press; then setting the pressure of the cubic hydraulic press to enable a hammer of the cubic hydraulic press to compact pyrophyllite, directly pressurizing the pressure of the cubic hydraulic press to 6GPa, gradually increasing the temperature of the cubic hydraulic press, wherein the temperature changes by about 30-40 ℃ every time, and the temperature change time stays for about 15min every time until the temperature of the cubic hydraulic press reaches 800 ℃; after reaching the preset test environment, the mixture of the magnesium alloy and the boron powder is sintered under high pressure in the environment of 6GPa and 800 ℃ for about 10-30min, after reaching the preset time, the heating is stopped, the mixture is cooled in a cubic hydraulic press for 30min, finally, the pressure of the cubic hydraulic press is unloaded, and the final test product is taken out, so that the metal boride to be treated is obtained.
S2, pretreating the strong acid type high-molecular polymer, wherein the related chemical equation is (MgLi)xB2+2H+→2HB+Mg2+：
Firstly, controlling the room temperature to be about 20 ℃, putting a strong acid type high molecular polymer into deionized water prepared before an experiment for washing, and soaking for 5 hours; then, the strong acid type high molecular polymer soaked by deionized water is put into dilute sulfuric acid diluted into 2-5% by volume by concentrated sulfuric acid and soaked for 5 hours; then taking out the strong acid type high molecular polymer from the dilute sulfuric acid, and then putting the high molecular polymer into deionized water for washing until the strong acid type high molecular polymer is detected to be neutral by a pH meter; and finally, taking out the strong acid type high molecular polymer, and putting the high molecular polymer in room temperature for air drying for later experiments.
S3, ion exchange, wherein the chemical formula involved is,
firstly, controlling the room temperature to be about 20 ℃, mixing a metal boride and a strong acid type high polymer according to the mass ratio of 1:1-10, and placing the mixture in a conical flask filled with magnetons; then adding 200mL of polar organic solvent and 10mg of inorganic salt solid into a conical flask filled with the metal boride and the strong acid type high molecular polymer; then, stirring the mixed solution by using a magnetic stirrer at the same room temperature, and reacting the mixed solution for about 12-48 h; then, filtering unreacted metal boride and high molecular polymer by using a vacuum filtration device, and retaining the borohydride solution after reaction; then, carrying out vacuum treatment on the borohydride solution by using a vacuum pump carried by a rotary evaporator, and pumping the polar organic solvent out of the borohydride solution when the set pressure value is about-0.1 MPa, so as to only leave borohydride powder; and finally, drying the borohydride powder in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain the borohydride powder.
S4, electron beam irradiation decomposition:
first pass N2Then using electron beam energy emitters at N2And (3) under the atmosphere, irradiating the borohydride powder for a certain time by 5-20kV electron beams to obtain the final boron alkene nanosheet.
In step S1, the magnesium alloy may be magnesium lithium alloy (MgLi), magnesium sodium alloy (MgNa), or magnesium potassium alloy (MgK) to improve the activity of magnesium and increase active sites.
In step S2, the strong acid type high polymer may be polyvinyl benzene sulfonic acid or sulfonic styrene-divinylbenzene copolymer as a carrier for ion exchange.
In step S3, the polar organic solution may be acetonitrile, methanol or ethanol to control the hydrogen ion release rate.
In step S3, the inorganic salt may be sodium chloride, magnesium chloride, potassium chloride or calcium chloride to accelerate the release rate of hydrogen ions.
In step S4, the electron beam irradiation time is 30-60 min.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, a method for rapidly preparing a bidimensional borane according to the present invention is further described with reference to the following examples:
example 1:
s1, preparing the metal boride to be treated: headFirstly, respectively weighing 0.5g of magnesium-lithium alloy and 1g of boron powder by using a balance according to the mass ratio of 1:2, wherein the magnesium-lithium alloy can improve the activity of magnesium and increase the active sites of the magnesium; and (3) encapsulating a mixture of 0.5g of magnesium-lithium alloy and 1g of boron powder in pyrophyllite, and placing a well-mixed sample at a hammer head of a cubic hydraulic press. Firstly, setting the pressure of a cubic hydraulic press, enabling a hammer head of the cubic hydraulic press to compact pyrophyllite, and directly pressurizing the pressure of the cubic hydraulic press to the required pressure, wherein the pressure value is 6 GPa; and gradually increasing the temperature of the cubic hydraulic press, wherein the range of each temperature change is 30-40 ℃, and the time of each temperature change is kept for about 15min until the temperature of the cubic hydraulic press reaches the required temperature, and the temperature value is 800 ℃. Finally, after reaching the preset test environment, placing the mixture of 0.5g of magnesium-lithium alloy and 1g of boron powder encapsulated in pyrophyllite in an environment with 6GPa and 800 ℃, sintering at high pressure for about 10-30min, stopping heating after reaching the preset time, cooling the sintered product in a cubic hydraulic press for 30min, unloading the pressure of the cubic hydraulic press, and taking out the final test product to obtain the metal boride (MgLi) to be treatedxB2。
S2, pretreatment of a strong acid type high polymer: firstly, weighing 3g of polyvinyl benzene sulfonic acid by using a balance, wherein the polyvinyl benzene sulfonic acid is used as a carrier for carrying out ion exchange; controlling the room temperature to be about 20 ℃, putting the polyvinyl benzene sulfonic acid into deionized water prepared before the experiment for water washing, and soaking for 5 hours; then, putting the polyvinyl benzene sulfonic acid soaked by the deionized water into dilute sulfuric acid diluted by concentrated sulfuric acid and having the volume fraction of 2-5%, and soaking for 5 hours; and then taking out the polyvinylbenzenesulfonic acid from the dilute sulfuric acid, then putting the polyvinylbenzenesulfonic acid into deionized water for washing again until the polyvinylbenzenesulfonic acid is detected to be neutral by using a pH meter, and finally taking out the polyvinylbenzenesulfonic acid, and putting the polyvinylbenzenesulfonic acid at room temperature for air drying for later experiments.
S3, ion exchange: first, 1g of (MgLi) was weighed out on a balance at a mass ratio of 1:3xB2And 3g of polyvinylbenzenesulfonic acid, 1g of (MgLi) at room temperature around 20 DEG CxB2Mixing with 3g of polyvinyl benzene sulfonic acid, and placing in a conical flask filled with magnetons; then respectively adding 200mL of acetonitrile and 10mg of sodium chloride into the conical flask, wherein the acetonitrile is mainly used for controlling the release rate of hydrogen ions, and the sodium chloride is mainly used for promoting the release of the hydrogen ions; then, stirring the solution at the room temperature by a magnetic stirrer at the rotating speed of 300r/min through magnetons, and reacting the mixed solution for about 24 hours; after the stirring was completed, unreacted (MgLi) was filtered off by a vacuum filtration apparatusxB2And polyvinylbenzenesulfonic acid, and reserving the borohydride solution after the reaction; then, carrying out vacuum treatment on the borohydride solution by using a vacuum pump carried by a rotary evaporator, and pumping acetonitrile out of the borohydride solution when the set pressure value is about-0.1 MPa, so as to only leave borohydride powder; and finally, drying the borohydride powder in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain borohydride.
S4, electron beam irradiation decomposition: first pass N2Then using electron beam energy emitters at N2And (3) under the atmosphere, irradiating the borohydride powder for 60min by using an electron beam of 5kV to obtain the final boron alkene nanosheet.
Experimental phenomena of example 1:
the X-ray diffraction (XRD) technology can be used for measuring the lattice constant of the crystal so as to determine the element types, and is commonly used for qualitative analysis and quantitative analysis of phase.
In order to determine the type of the final test product, the lattice constant of the final test product is determined by using an X-ray diffraction technique, as shown in FIG. 1, the horizontal axis of XRD is 2 theta, and the radiation collected by the probe is subjected to the 2 theta angle every time the sample rotates by an theta angle in a continuous scanning mode; the ordinate is the absorption intensity of the sample. From an XRD (X-ray diffraction) diagram, an amorphous phase diffraction peak of boron and a boron hydride exists at 15-25 ℃, and the result proves that the boron hydride is generated by the reaction.
The most important analysis functions of a Scanning Electron Microscope (SEM) are: an X-ray microscopic analysis system (i.e. spectrometer, EDS) is mainly used for qualitative and quantitative analysis of elements and can analyze information such as chemical components of sample micro-areas; an electron back scattering system (i.e., a crystallography analysis system) is mainly used for the research of crystals and minerals.
In order to observe the morphology of the final test product, the scanning electron microscope technology is used for observing the final borolene nanosheet, as shown in fig. 2, from an SEM image, we can observe the nanosheet in a two-dimensional lamellar manner, which proves that the reaction obtains the two-dimensional borolene.
Example 2:
s1, preparing the metal boride to be treated: firstly, respectively weighing 0.5g of magnesium-sodium alloy and 1g of boron powder by using a balance according to the mass ratio of 1:2, wherein the magnesium-sodium alloy can improve the activity of magnesium and increase the active sites of the magnesium; and (3) encapsulating a mixture of 0.5g of magnesium-sodium alloy and 1g of boron powder in pyrophyllite, and placing a sample at the hammer head of a cubic hydraulic press. The pressure of the cubic hydraulic press is set firstly, so that the hammer head of the cubic hydraulic press compacts the pyrophyllite. Then, processing the magnesium-sodium alloy and the boron powder packaged in the pyrophyllite by using a cubic hydraulic press, firstly setting the pressure of the cubic hydraulic press, and directly pressurizing the pressure to the required pressure, wherein the pressure value is 6 GPa; and gradually increasing the temperature of the cubic hydraulic press, wherein the temperature change range of each time is 30-40 ℃, and the time of each temperature change is kept for about 15min until the temperature of the cubic hydraulic press reaches the required temperature, and the temperature value is 800 ℃. Finally, after reaching the preset test environment, placing the mixture of 0.5g of magnesium-sodium alloy and 1g of boron powder encapsulated in pyrophyllite in an environment with 6GPa and 800 ℃, sintering at high pressure for about 10-30min, stopping heating after reaching the preset time, cooling the sintered product in a cubic hydraulic press for 30min, unloading the pressure of the cubic hydraulic press, and taking out the final test product to obtain the metal boride (MgNa) to be treatedxB2。
S2, pretreatment of a strong acid type high polymer: firstly, weighing 5g of sulfonic styrene-divinylbenzene copolymer by using a balance, wherein the sulfonic styrene-divinylbenzene copolymer is used as a carrier for ion exchange; controlling the room temperature to be about 20 ℃, putting the sulfonic styrene-divinylbenzene copolymer into deionized water prepared before an experiment for water washing, and soaking for 5 hours; then, putting the sulfonic styrene-divinylbenzene copolymer soaked by deionized water into dilute sulfuric acid with the volume fraction of 2-5% diluted by concentrated sulfuric acid, and soaking for 5 hours; and then taking out the sulfonic styrene-divinylbenzene copolymer from the dilute sulfuric acid, then putting the sulfonic styrene-divinylbenzene copolymer into deionized water for washing again until the sulfonic styrene-divinylbenzene copolymer is detected to be neutral by a pH meter, and finally taking out the sulfonic styrene-divinylbenzene copolymer, and putting the sulfonic styrene-divinylbenzene copolymer into room temperature for air drying for later experiments.
S3, ion exchange: firstly, 1g of (MgNa) is weighed by a balance according to the mass ratio of 1:5xB2And 5g of a sulfostyrene-divinylbenzene copolymer, 1g of (MgNa)xB2And 5g of sulfonic styrene-divinylbenzene copolymer are mixed and placed in a conical flask filled with magnetons; then respectively adding 200mL of methanol and 10mg of sodium chloride into the conical flask, wherein the methanol is mainly used for controlling the release rate of hydrogen ions, and the sodium chloride is mainly used for promoting the release of the hydrogen ions; then, stirring the solution at the room temperature by a magnetic stirrer at the rotating speed of 300r/min through magnetons, and reacting the mixed solution for about 24 hours; after the stirring was completed, unreacted (MgNa) was filtered off by a vacuum filtration apparatusxB2And sulfonic styrene-divinylbenzene copolymer, and reserving the borohydride solution after reaction; then, carrying out vacuum treatment on the borohydride solution by using a vacuum pump carried by a rotary evaporator, and pumping the methanol out of the borohydride solution when the set pressure value is about-0.1 MPa, so as to only leave borohydride powder; and finally, drying the borohydride powder in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain borohydride.
S4, electron beam irradiation decomposition: first pass N2Then using electron beam energy emitters at N2And (3) under the atmosphere, irradiating the borohydride powder for 50min by using an electron beam of 10kV to obtain the final boron alkene nanosheet.
Example 3:
s1, preparing the metal boride to be treated: firstly, respectively weighing 0.5g of magnesium-potassium alloy and 1g of boron powder by using a balance according to the mass ratio of 1:2, wherein the magnesium-potassium alloy can improve the activity of magnesium and increase the active sites of the magnesium; and (3) encapsulating a mixture of 0.5g of magnesium-potassium alloy and 1g of boron powder in pyrophyllite, and placing a sample at the hammer head of a cubic hydraulic press. The pressure of the cubic hydraulic press is set firstly, so that the hammer head of the cubic hydraulic press compacts the pyrophyllite. Then, processing the magnesium-potassium alloy and the boron powder packaged in the pyrophyllite by using a cubic hydraulic press, firstly setting the pressure of the cubic hydraulic press, and directly pressurizing the pressure to the required pressure, wherein the pressure value is 6 GPa; and gradually increasing the temperature of the cubic hydraulic press, wherein the temperature change range of each time is 30-40 ℃, and the time of each temperature change is kept for about 15min until the temperature of the cubic hydraulic press reaches the required temperature, and the temperature value is 800 ℃. Finally, after reaching the preset test environment, placing the mixture of 0.5g of magnesium-potassium alloy and 1g of boron powder encapsulated in pyrophyllite in an environment with 6GPa and 800 ℃, sintering at high pressure for about 10-30min, stopping heating after reaching the preset time, cooling the sintered product in a cubic hydraulic press for 30min, unloading the pressure of the cubic hydraulic press, and taking out the final test product to obtain the metal boride (MgK) to be processedxB2。
S2, pretreatment of a strong acid type high polymer: firstly, weighing 7g of polyvinyl benzene sulfonic acid by using a balance, wherein the polyvinyl benzene sulfonic acid is used as a carrier for carrying out ion exchange; controlling the room temperature to be about 20 ℃, putting the polyvinyl benzene sulfonic acid into deionized water prepared before the experiment for water washing, and soaking for 5 hours; then, putting the polyvinyl benzene sulfonic acid soaked by the deionized water into dilute sulfuric acid diluted by concentrated sulfuric acid and having the volume fraction of 2-5%, and soaking for 5 hours; and then taking out the polyvinylbenzenesulfonic acid from the dilute sulfuric acid, then putting the polyvinylbenzenesulfonic acid into deionized water for washing again until the polyvinylbenzenesulfonic acid is detected to be neutral by using a pH meter, and finally taking out the polyvinylbenzenesulfonic acid, and putting the polyvinylbenzenesulfonic acid at room temperature for air drying for later experiments.
S3, ion exchange: firstly, according to the mass ratio of1:7 ratio, 1g of (MgK) are weighed out separately on a balancexB2And 7g of polyvinylbenzenesulfonic acid, 1g of (MgK)xB2Mixing with 7g of polyvinyl benzene sulfonic acid and placing in a conical flask filled with magnetons; then respectively adding 200mL of ethanol and 10mg of sodium chloride into the conical flask, wherein the ethanol is mainly used for controlling the release rate of hydrogen ions, and the sodium chloride is mainly used for promoting the release of the hydrogen ions; then, stirring the solution at the room temperature by a magnetic stirrer at the rotating speed of 300r/min through magnetons, and reacting the mixed solution for about 24 hours; after the stirring was completed, unreacted (MgK) was filtered off by a vacuum filtration apparatusxB2And polyvinylbenzenesulfonic acid, and reserving the borohydride solution after the reaction; then, carrying out vacuum treatment on the borohydride solution by using a vacuum pump carried by a rotary evaporator, and pumping the ethanol out of the borohydride solution when the set pressure value is about-0.1 MPa, so as to only leave borohydride powder; and finally, drying the borohydride powder in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain borohydride.
S4, electron beam irradiation decomposition: first pass N2Then using electron beam energy emitters at N2And (3) under the atmosphere, irradiating the borohydride powder for 30min by an electron beam of 15kV to obtain the final boron alkene nanosheet.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (7)
1. A method for rapidly preparing two-dimensional borolene comprises a metal boride preparation process, a strong acid type high polymer pretreatment process, an ion exchange process and an irradiation decomposition process, and is characterized by comprising the following steps:
s1, preparing the metal boride to be treated: firstly, encapsulating a mixture of magnesium alloy and boron powder in pyrophyllite according to a mass ratio of 1:2, and placing a sample at a hammer head of a cubic hydraulic press; setting the pressure of the cubic hydraulic press, enabling a hammer of the cubic hydraulic press to compact pyrophyllite, directly pressurizing to 6GPa, gradually increasing the temperature of the cubic hydraulic press, wherein the temperature changes by 30-40 ℃ every time, and the temperature changes for 15min every time until the temperature of the cubic hydraulic press reaches 800 ℃; after reaching the preset test environment, sintering the mixture of the magnesium alloy and the boron powder under high pressure for 10-30min under the environment of 6GPa and 800 ℃, stopping heating, cooling for 30min in a cubic hydraulic press, releasing pressure, and taking out a final test product to obtain a metal boride to be treated;
s2, pretreatment of a strong acid type high polymer: firstly, controlling the room temperature at 20 ℃, putting a strong acid type high molecular polymer into deionized water prepared before an experiment for water washing, and soaking for 5 hours; then, the strong acid type high molecular polymer soaked by deionized water is put into dilute sulfuric acid diluted into 2-5% by volume by concentrated sulfuric acid and soaked for 5 hours; then taking out the strong acid type high molecular polymer from the dilute sulfuric acid, then putting the high molecular polymer into deionized water for washing until the strong acid type high molecular polymer is detected to be neutral by a pH meter, and finally taking out the strong acid type high molecular polymer, and putting the high molecular polymer at room temperature for air drying for later experiments;
s3, ion exchange: firstly, mixing metal boride and a strong acid type high polymer at the room temperature of 20 ℃ according to the mass ratio of 1:1-10, and placing the mixture into a conical flask filled with magnetons; then adding 200mL of polar organic solvent and 10mg of inorganic salt solid into the conical flask, wherein the inorganic salt solid is mainly used for promoting the release of hydrogen ions; then, stirring the solution by using a magnetic stirrer at room temperature to enable the mixed solution to react for 12-48 h; then, filtering unreacted metal boride and high molecular polymer by using a vacuum filtration device, and retaining the borohydride solution after reaction; then, carrying out vacuum treatment on the borohydride solution by using a vacuum pump carried by a rotary evaporator, and pumping the polar organic solvent out of the borohydride solution when the set pressure value is-0.1 MPa, so as to only leave borohydride powder; finally, drying the borohydride powder in a vacuum drying oven at the temperature of 40 ℃ for 12 hours to obtain borohydride; and
s4, electron beam irradiation decomposition: first pass N2Then using electron beam energy emitters at N2And (3) under the atmosphere, irradiating the borohydride powder for a certain time by 5-20kV electron beams to obtain the final boron alkene nanosheet.
2. The method for rapidly preparing two-dimensional borane according to claim 1, wherein in the step S1, the magnesium alloy is magnesium-lithium alloy, magnesium-sodium alloy or magnesium-potassium alloy.
3. The method according to claim 1, wherein in step S2, the strong acid type high polymer is polyvinylbenzenesulfonic acid or sulfonic styrene-divinylbenzene copolymer as a carrier for ion exchange.
4. The method for rapidly preparing two-dimensional borane according to claim 1, wherein the polar organic solution is acetonitrile, methanol or ethanol in step S3.
5. The method for rapidly preparing bidimensional borane according to claim 1, characterized in that in step S3, the inorganic salt is sodium chloride, magnesium chloride, potassium chloride or calcium chloride.
6. The method for rapidly preparing two-dimensional borane according to claim 1, wherein the electron beam irradiation time period in step S4 is 30-60 min.
7. The method for rapidly preparing two-dimensional borane according to claim 1, wherein the chemical equation involved in the step S1 is as follows:
the chemical equation involved in step S2 is:
(MgLi)xB2+2H+→2HB+Mg2+
the chemical equation involved in step S3 is:
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