CN113233470B - Two-dimensional transition metal boride material, and preparation method and application thereof - Google Patents
Two-dimensional transition metal boride material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a two-dimensional transition metal boride material, and a preparation method and application thereof. The molecular formula of the two-dimensional transition metal boride material is represented as MB or M n B 2n‑2 M is selected from the group consisting of the early transition metals Mn, W, or a combination of any two or more of Mn, W and Cr, Fe, Mo, B is boron, and n is 2, 3 or 4. The two-dimensional transition metal boride has a tetragonal crystal structure and a space group of Cmmm. The invention also provides a preparation method of the two-dimensional transition metal boride material by etching the MAB phase in a dilute alkali solution. The layered material of the two-dimensional transition metal boride material provided by the invention has a series of advantages of adjustable magnetism, heat conduction, electric conduction, multiple active sites and the like, and the structure and the property of the layered material are regulated and controlled by regulating and controlling the content, the position and the type of an M-site element; and the preparation process is simple and easy to operate, and has potential application prospects in the fields of wave absorption, energy storage, catalysis and the like.
Description
Technical Field
The invention relates to an inorganic material, in particular to a two-dimensional transition metal boride material as well as a preparation method and application thereof, belonging to the technical field of materials.
Background
MBenes are novel two-dimensional transition metal boride materials, similar to two-dimensional transition metal carbide (nitride) MXenes, and MBenes nanosheets can be theoretically transformed by the A site of a mother phase MAB phase (M refers to a transition metal element, A is a main group element, and B is boron)Chemical etching is carried out, and the following physical stripping is matched to obtain [ J.Mater.Chem.A,2017,5: 23530-; chem. mater.,2017,29:8953-8957 ]. More than 20 MAB phases are synthesized at present, including MoAlB, WAlB and Fe 2 AlB 2 、Cr 2 AlB 2 、Mn 2 AlB 2 、Cr 3 AlB 4 、Cr 4 AlB 6 、(Mo x ,Cr 1-x )AlB、(Mo x ,W 1-x )AlB、(Fe 2 ,Cr 2-x )AlB 2 And the like. Wherein when n is 1, for example, MoAlB and WAlB space group is Cmcm, and the crystal structure thereof is represented by M 2 B 2 The sub-crystal structure and 2 Al atomic layers are stacked alternately. When n is 2-4, the general formula may be represented by Mn A B 2n-2 The space group is Cmmm, and the crystal structure is formed by M n B 2n-2 And 1 atomic layer of Al are stacked alternately [ J.Am.chem.Soc.,2018,140: 8833-. There is relatively little research on MBenes, although Fe has been predicted theoretically 2 B 2 、Mn 2 B 2 、Cr 2 B 2 And the like, however, only for Cr 2 AlB 2 Chemical etching was reported, as well as partial etching of the Al atomic layer in the MoAlB phase.
The Zhou Yan Chun investigator team at The institute for aerospace materials and technology (CrB) [ J.Mater.Sci.Technol.,2018,34: 2022-2026 ] and The teaching team of Raymond E.Schaak of The Pennsylvania State University (MoB) [ chem.Mater.,2017,29: 8953-8957; J.Am.chem.Soc.2018,140:8833-8840 ] respectively prepared from corresponding MAB parent phase (Cr) by 1.25M dilute hydrochloric acid and 10% NaOH or LiF/HCl mixed solution at room temperature 2 AlB 2 MoAlB), produced accordion-like MBenes particles. Among them, professor team of Raymond e.schaak found that 2 layers of Al atoms in MoAlB exhibited a topochemical pull-off phenomenon during etching. In the early stage of etching, the single-layer Al atoms are extracted to ensure that the MoAlB local crystal structure is gradually converted into Mo 6 Al 5 B 6 、Mo 4 Al 3 B 4 、Mo 3 Al 2 B 3 Or Mo 2 AlB 2 Finally they predict the possible pass of Mo 2 AlB 2 And etching the phase to obtain the MBenes material of MoB type. Mo is predicted by the Sunzhimei professor team of Beijing aerospace university through the density functional theory 2 B 2 And Fe 2 B 2 Potential application in the fields of lithium ion batteries and electrocatalysis [ J.Mater.Chem.A,2017,5: 23530-. They found that lithium ions are in two-dimensional Mo 2 B 2 And Fe 2 B 2 All directions have very small energy barrier during diffusion, and the minimum energy barrier is 0.27eV (Mo) 2 B 2 ) And 0.24eV (Fe) 2 B 2 ) The same common LIB electrode materials of graphite (0.4eV), graphene (0.277eV) and MoS 2 (0.22eV)、Ti 3 C 2 MXenes (0.28eV) were close. But two-dimensional Mo 2 B 2 And Fe 2 B 2 The theoretical specific capacity can reach 444mAh/g (Mo) 2 B 2 ) And 665mAh/g (Fe) 2 B 2 ) Is superior to Ti 3 C 2 MXenes(～320mAh/g)、Ca 2 N (-320 mAh/g) and graphite (-372 mAh/g). Two-dimensional Mo 2 B 2 And Fe 2 B 2 The Gibbs free energy of hydrogen adsorption (Δ GH) is nearly zero, indicating that it has good catalytic activity for hydrogen evolution reaction. The Zhao Ji Jun professor team of the university of major theory of technology utilizes the density functional theory to screen MnB, HfB, ZrB and Au 2 B、Mo 2 B、Nb 5 B 2 、Nb 3 B 4 、Ta 3 B 4 、V 3 B 4 、OsB 2 、FeB 2 And RuB 2 Ferromagnetic [ Nanoscale horiz, 2018,3: 335-341 ]. They found that two-dimensional MnB has a higher Curie temperature (345K) and a stronger metallic ferromagnetism (3.2 μ B/Mn). Meanwhile, functionalization by-F and-OH helps to raise the Curie temperature (405K and 600K) of the post-two-dimensional MnB.
In conclusion, theoretical research shows that MBenes materials have excellent intrinsic magnetic properties which are not possessed by other common two-dimensional materials, so that MBenes has unique research value in the field of two-dimensional material functional application. However, research on the MBenes material is still in the initial stage, and the research on the synthesis mechanism, the structural stability, the influence of the surface functional group and the like of the MBenes material is still lack of systematic research.
Disclosure of Invention
The invention mainly aims to provide a two-dimensional transition metal boride material, a preparation method and application thereof, thereby overcoming the defects in the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a two-dimensional transition metal boride material, the molecular formula of which is MB or M n B 2n-2 Wherein M is any one or any combination of more than two of the elements in the early transition metal group, B is boron, and n is 2, 3 or 4.
In some embodiments, M is any one of Mn or W, or a combination of both.
Further, in addition to Mn, W, the M may include any one or any combination of two or more of Cr, Fe, Mo, and the like.
The embodiment of the invention also provides a preparation method of the two-dimensional transition metal boride material, which comprises the following steps: and removing the A site element in the MAB phase material by adopting a dilute alkali solution etching reaction to obtain the two-dimensional transition metal boride material.
Further, the preparation method comprises the following steps: and etching the MAB phase material in a dilute alkali solution with the concentration of 0.1-2 mol/L for 0.5-24 h, and stripping the A-site Al element of the MAB phase material to obtain the two-dimensional transition metal boride material.
The embodiment of the invention also provides application of the two-dimensional transition metal boride material in the fields of wave absorption, energy storage, catalysis and the like. Compared with the prior art, the invention has the beneficial effects that:
the layered material of the two-dimensional transition metal boride material provided by the invention has a series of advantages of adjustable magnetism, heat conduction, electric conduction, multiple active sites and the like, and the structure and the property of the layered material are regulated and controlled by regulating and controlling the content, the position and the type of an M-site element; and the preparation process is simple and easy to operate, and has potential application prospects in the fields of wave absorption, energy storage, catalysis and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows Mn in example 1 of the present invention 2 AlB 2 XRD pattern after diluted alkali etching;
FIGS. 2a and 2b are Mn in example 1 of the present invention 2 AlB 2 SEM pictures before and after diluted alkali etching;
FIGS. 3 and 4 are Mn obtained in example 1 of the present invention 2 B 2 The normal temperature magnetization curve and the susceptibility curve chart of the material.
Detailed Description
The two-dimensional transition metal boride material synthesized by the method has very important significance for expanding the variety of two-dimensional materials and regulating and controlling the chemical properties of substances; secondly, by utilizing the characteristic that M-site elements of the MAB phase material can form alloy compounds with other elements, the M-site solid-dissolved brand new MAB phase material can be synthesized, can be used as a precursor of the two-dimensional transition metal boride, is an innovation in material synthesis means, and provides a brand new synthesis strategy for the synthesis of other two-dimensional transition metal borides; in addition, the structure and the property of the two-dimensional transition metal boride material are regulated and controlled by regulating and controlling the content, the position and the type of the M-site element, so that the application purpose of the two-dimensional transition metal boride material in the fields of wave absorption, energy storage, catalysis and the like is achieved.
An aspect of an embodiment of the present invention provides a two-dimensional transition metal boride represented by a molecular formula of MB or M n B 2n-2 Wherein M is selected from any one or any combination of more than two of elements in an early transition metal group, B is boron, and n is 2, 3 or 4.
In some embodiments, the M includes transition metals Mn, W, or alloys of Mn, W and any two or more of Cr, Fe, and Mo, and is not limited thereto.
In some embodiments, B is boron.
Further, the two-dimensional transition metal boride has a tetragonal structure and a space group of Cmmm.
Further, the two-dimensional transition metal boride has good magnetic, electrical and thermal properties.
For example, preliminary studies have found that Mn 2 B 2 The material shows magnetic behavior at normal temperature.
Another aspect of the embodiments of the present invention provides a method for preparing a two-dimensional transition metal boride, including: and removing the A site element in the MAB phase material by adopting a dilute alkali solution etching reaction to obtain the two-dimensional transition metal boride material.
In some embodiments, the method of making comprises: and etching and reacting the MAB phase material in a dilute alkali solution with the concentration of 0.1-2 mol/L for 0.5-24 h, and stripping the A-site Al element of the MAB phase to obtain the two-dimensional transition metal boride material.
The preparation method of the MAB phase material comprises the following steps: and uniformly mixing the M and/or M-containing material, the A and/or A-containing material and the B and/or B-containing material according to the molar ratio of the target materials, and reacting the obtained mixture at the high temperature of 1000-1200 ℃ for 6-12 h in an inert atmosphere to obtain the MAB phase material.
Further, the molecular formula of the MAB phase material is expressed as MAB or M n AB 2n-2 Wherein M is selected from any one or any combination of more than two of the transition metal groups, B is boron, and n is 2, 3 or 4.
In some embodiments, the M includes transition metals Mn, W, or alloys of Mn, W and any two or more of Cr, Fe, and Mo, and is not limited thereto.
In some embodiments, the M-containing material includes, but is not limited to, elemental M-containing and/or M-containing alloys.
Further, the a-containing material includes an aluminum-containing simple substance and/or an aluminum-containing alloy, but is not limited thereto.
Further, the B-containing material includes, but is not limited to, elemental boron-containing and/or boron-containing alloys.
Further, inorganic salts such as sodium chloride and potassium chloride can be added in the preparation process of the MAB phase material.
Further, the alkaline substance contained in the dilute alkaline solution includes any one or a combination of two or more of alkaline solutions such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ammonium hydroxide, and the like, but is not limited thereto.
Further, the concentration of the alkaline substance in the dilute alkali solution is 0.1-2 mol/L.
Furthermore, the etching reaction time is 0.5-24 h, and the temperature is 15-40 ℃. The invention adopts alkali liquor etching to meet the requirement of certain material systems which cannot be stabilized in the conventional acid-washing etching environment, such as Mn 2 AlB 2 The material will dissolve completely in the pickling system.
The embodiment of the invention also provides application of any one of the two-dimensional transition metal boride materials in the fields of wave absorption, energy storage, catalysis and the like.
The present invention will be described in further detail with reference to the following examples and accompanying drawings, which are provided for the purpose of facilitating understanding of the present invention and are not intended to limit the present invention in any way.
Example 1: in this example, M is Mn 2 B 2 A material.
The Mn is 2 B 2 The preparation method of the material comprises the following steps:
(1) 2.20g of manganese powder with the particle size of 1 mu m, 0.65g of 200-mesh aluminum powder, 0.43g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride are weighed and ground and mixed to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 6h, and the inert atmosphere is used for protection. And taking out the reaction product in the alumina crucible after the temperature of the sintering system is reduced to room temperature.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
(4) Newly synthesized Mn 2 AlB 2 The powder was ground to 500 mesh and diluted KOH solution (0.5mol/L) at 1gMn 2 AlB 2 The powder is mixed evenly according to the proportion of 200ml solution and reacts for 0.5h under the protection of Ar atmosphere.
(5) And (3) washing the powder treated by the dilute KOH solution by using deionized water, performing suction filtration, drying in vacuum, and storing in a glove box. Referring to fig. 1, it can be seen that a series of new peaks appear at 11.6 °, 23.4 °, etc., which correspond to the bragg equation, 2dsin θ ═ n λ, and thus it is very likely that the same crystal plane system of the same new material is represented. Meanwhile, a weak new peak is found only at 33.6 degrees and 38.2 degrees through searching, and the weak new peak possibly belongs to the new substance. Therefore, it can be judged that the obtained novel substance is highly likely to have a clearly preferred orientation. The above judgment was confirmed by SEM observation, and it was found that the bulk of Mn was present 2 AlB 2 The powder particles are covered with a layer of about 1-3 μm flakes (parallel as in fig. 2b) or honeycomb flakes (at an angle to the surface as in fig. 2b) on the surface. This is quite different from the original surface, which is smooth (fig. 2 (a)). The above-mentioned flake was analyzed by energy spectroscopy and found to contain Mn, Al, B, C, O and Au (gold spraying treatment). Comparison of Mn without acid-base aftertreatment 2 AlB 2 The powder energy spectrum analysis can find that the flake is aluminum-deficient Mn with oxygen-containing functional groups on the surface 2 B 2 A sheet.
Further, magnetization curve analysis (FIGS. 3 and 4) showed such Mn 2 B 2 The flake presents intrinsic superparamagnetism at normal temperature, which is rare in two-dimensional materials at present.
Table 2 EDS analysis of selected regions of fig. 2
Examples2: in this example, M is Mn 2 B 2 A material. The concentration of the etchant is adjusted to 1 mol/L.
The Mn is 2 B 2 The preparation method of the material comprises the following steps:
(1) 2.20g of manganese powder with the particle size of 1 mu m, 0.65g of 200-mesh aluminum powder, 0.43g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride are weighed and ground and mixed to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1050 ℃, the heat preservation time is 6h, and the inert atmosphere is used for protection. And after the temperature of the sintering system is reduced to room temperature, taking out a reaction product in the alumina crucible.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
(4) Newly synthesized Mn 2 AlB 2 The powder was ground to 500 mesh and diluted barium hydroxide solution (1mol/L) with 1g Mn 2 AlB 2 The powder is mixed evenly according to the proportion of 200ml solution and reacts for 0.5h under the protection of Ar atmosphere.
(5) And (3) washing the powder treated by the dilute barium hydroxide solution by using deionized water, performing suction filtration, vacuum drying and storing in a glove box. As shown in FIG. 1, the target Mn can be obtained even at this etchant concentration 2 B 2 A material.
Example 3: in this embodiment, the M site is a WB material of tungsten element.
The preparation method of the WB material is as follows:
(1) 2.76g of tungsten powder with the particle size of 1 mu m, 0.40g of 200-mesh aluminum powder, 0.16g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride are weighed and ground and mixed to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1150 ℃, the heat preservation time is 12h, and the inert atmosphere is used for protection. And taking out the reaction product in the alumina crucible after the temperature of the sintering system is reduced to room temperature.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then cleaning the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking out the reaction product after 12 hours to obtain a solid product.
(4) The newly synthesized WAlB powder is ground to 500 meshes, and is uniformly mixed with a diluted KOH solution (2mol/L) according to the proportion of 1g of WAlB powder to 200ml of solution, and the mixture is reacted for 24 hours under the protection of Ar atmosphere.
(5) And washing the powder treated by the diluted KOH solution by using deionized water, performing suction filtration, vacuum drying and storing in a glove box.
Example 4: in this example, M site is tungsten element and molybdenum element (W) 0.5 Mo 0.5 ) And (B) material.
The (W) 0.5 Mo 0.5 ) The preparation method of the material B comprises the following steps:
(1) 1.38g of tungsten powder with the particle size of 1 mu m, 0.72g of molybdenum powder with the particle size of 2-3 mu m, 0.40g of 200-mesh aluminum powder, 0.16g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride are weighed and ground and mixed to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1100 ℃, the heat preservation time is 6h, and the inert atmosphere is used for protection. And after the temperature of the sintering system is reduced to room temperature, taking out a reaction product in the alumina crucible.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then washing the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking the reaction product out after 12 hours to obtain a solid product.
(4) Will newly synthesize (W) 0.5 Mo 0.5 ) AlB powder was ground to 500 mesh and diluted ammonium hydroxide solution (1mol/L) at 1g (W) 0.5 Mo 0.5 ) The AlB powder is evenly mixed with 200ml of solution, and the mixture is reacted for 12 hours under the protection of Ar atmosphere.
(5) And washing the powder treated by the dilute ammonium hydroxide solution by using deionized water, performing suction filtration, vacuum drying and storing in a glove box.
Example 5: in this example, M site is manganese element and chromium element (Mn) 0.5 Cr 0.5 ) 2 B 2 A material.
The (Mn) 0.5 Cr 0.5 ) 2 B 2 The preparation method of the material comprises the following steps:
(1) weighing 0.82g of manganese powder with the particle size of 1 mu m, 0.78g of chromium powder with the particle size of 1 mu m, 0.405g of 200-mesh aluminum powder, 0.32g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride, and grinding and mixing the materials to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1200 ℃, the heat preservation time is 6h, and the inert atmosphere is used for protection. And taking out the reaction product in the alumina crucible after the temperature of the sintering system is reduced to room temperature.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then washing the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking the reaction product out after 12 hours to obtain a solid product.
(4) Newly synthesized (Mn) 0.5 Cr 0.5 ) 2 AlB 2 The powder was ground to 500 mesh and diluted calcium hydroxide solution (0.1mol/L) at 1g of (Mn) 0.5 Cr 0.5 ) 2 AlB 2 The powder is mixed evenly with 200ml solution, and the mixture is reacted for 6 hours under the protection of Ar atmosphere.
(5) And washing the powder treated by the dilute calcium hydroxide solution with deionized water, performing suction filtration, vacuum drying and storing in a glove box.
Example 6: in this example, M site is manganese and chromium (Mn) 0.5 Fe 0.5 ) 2 B 2 A material.
The (Mn) 0.5 Fe 0.5 ) 2 B 2 The preparation method of the material comprises the following steps:
(1) weighing 0.82g of manganese powder with the particle size of 1 mu m, 0.84g of iron powder with the particle size of 1 mu m, 0.405g of 200-mesh aluminum powder, 0.32g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride, and grinding and mixing the materials to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1000 ℃, the heat preservation time is 8h, and the inert atmosphere is used for protection. And after the temperature of the sintering system is reduced to room temperature, taking out a reaction product in the alumina crucible.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then washing the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking the reaction product out after 12 hours to obtain a solid product.
(4) Newly synthesized (Mn) 0.5 Fe 0.5 ) 2 AlB 2 The powder was ground to 500 mesh and washed with dilute NaOH solution (0.5mol/L) at 1g of (Mn) 0.5 Fe 0.5 ) 2 AlB 2 The powder is mixed evenly with 200ml solution, and the mixture is reacted for 3 hours under the protection of Ar atmosphere.
(5) And (4) washing the powder treated by the dilute NaOH solution with deionized water, performing suction filtration, vacuum drying and storing in a glove box.
Example 7: in this example, M site is manganese element and chromium element (Mn) 0.5 Cr 0.5 ) 3 B 4 A material.
The (Mn) 0.5 Cr 0.5 ) 3 B 4 The preparation method of the material comprises the following steps:
(1) weighing 0.82g of manganese powder with the particle size of 1 mu m, 0.78g of chromium powder with the particle size of 1 mu m, 0.27g of 200-mesh aluminum powder, 0.43g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride, and grinding and mixing the materials to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1200 ℃, the heat preservation time is 8h, and the inert atmosphere is used for protection. And taking out the reaction product in the alumina crucible after the temperature of the sintering system is reduced to room temperature.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then washing the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking the reaction product out after 12 hours to obtain a solid product.
(4) Newly synthesized (Mn) 0.5 Cr 0.5 ) 3 AlB 4 The powder was ground to 500 mesh and diluted KOH solution (1mol/L) at 1g of (Mn) 0.5 Cr 0.5 ) 3 AlB 4 The powder is mixed evenly with 200ml solution, and the mixture is reacted for 3 hours under the protection of Ar atmosphere.
(5) And (3) washing the powder treated by the dilute KOH solution by using deionized water, performing suction filtration, drying in vacuum, and storing in a glove box.
Example 8: in this example, M site is manganese and chromium (Mn) 0.5 Cr 0.5 ) 3 B 4 A material.
The (Mn) 0.5 Cr 0.5 ) 3 B 4 The preparation method of the material comprises the following steps:
(1) weighing 0.82g of manganese powder with the particle size of 1 mu m, 0.78g of chromium powder with the particle size of 1 mu m, 0.27g of 200-mesh aluminum powder, 0.43g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride, and grinding and mixing the materials to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1200 ℃, the heat preservation time is 8h, and the inert atmosphere is used for protection. And taking out the reaction product in the alumina crucible after the temperature of the sintering system is reduced to room temperature.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then washing the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking the reaction product out after 12 hours to obtain a solid product.
(4) Newly synthesized (Mn) 0.5 Cr 0.5 ) 3 AlB 4 The powder was ground to 500 mesh and diluted KOH solution (0.5mol/L) at 1g of (Mn) 0.5 Cr 0.5 ) 3 AlB 4 The powder is mixed evenly with 200ml solution, and the mixture is reacted for 3 hours under the protection of Ar atmosphere.
(5) And (3) washing the powder treated by the dilute KOH solution by using deionized water, performing suction filtration, drying in vacuum, and storing in a glove box.
Example 9: in this example, M site is manganese element and chromium element (Mn) 0.5 Cr 0.5 ) 4 B 6 A material.
The (Mn) 0.5 Cr 0.5 ) 4 B 6 The preparation method of the material comprises the following steps:
(1) 1.10g of manganese powder with the particle size of 1 mu m, 1.04g of chromium powder with the particle size of 1 mu m, 0.27g of 200-mesh aluminum powder, 0.65g of boron powder with the particle size of 2-3 mu m, 5.84g of sodium chloride and 7.45g of potassium chloride are weighed and ground and mixed to obtain a mixture.
(2) The mixture was placed in a tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 1200 ℃, the heat preservation time is 8h, and the inert atmosphere is used for protection. And after the temperature of the sintering system is reduced to room temperature, taking out a reaction product in the alumina crucible.
(3) Washing the reaction product with deionized water and alcohol: and putting the reaction product into a beaker, adding deionized water, stirring, ultrasonically cleaning for 30 minutes, standing for 1 hour, and pouring out the supernatant. And washing the reaction product for three times, then washing the reaction product with ethanol, putting the reaction product into an oven at 40 ℃, and taking the reaction product out after 12 hours to obtain a solid product.
(4) Newly synthesized (Mn) 0.5 Cr 0.5 ) 4 AlB 6 The powder was ground to 500 mesh and diluted KOH solution (2mol/L) at 1g of (Mn) 0.5 Cr 0.5 ) 3 AlB 4 The powder is mixed evenly with 200ml solution, and the mixture is reacted for 3 hours under the protection of Ar atmosphere.
(5) And washing the powder treated by the diluted KOH solution by using deionized water, performing suction filtration, vacuum drying and storing in a glove box. The properties of the layered materials of two-dimensional transition metal borides obtained in examples 3-9 of the invention were substantially the same as those of the products in examples 1-2.
In addition, the inventors of the present invention have conducted experiments by replacing the corresponding raw materials and process conditions in the foregoing examples 1 to 9 with the other raw materials and process conditions mentioned in the present specification, and as a result, it was revealed that a layered material of a two-dimensional transition metal boride can be obtained. In summary, the layered material of the two-dimensional transition metal boride provided by the embodiment of the invention has a series of advantages of adjustable magnetism, heat conduction, electric conduction, multiple active sites and the like, and the preparation process is simple and easy to operate, and has potential application prospects in the fields of wave absorption, energy storage, catalysis and the like.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (3)
1. The application of the two-dimensional transition metal boride material in the fields of wave absorption, energy storage or catalysis, and the preparation method of the two-dimensional transition metal boride material comprises the following steps: removing A-site elements in the MAB phase material by adopting a dilute alkali solution etching reaction to obtain the two-dimensional transition metal boride material, wherein alkaline substances contained in the dilute alkali solution are selected from any one or a combination of more than two of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and ammonium hydroxide, the concentration of the alkaline substances in the dilute alkali solution is 0.1-2 mol/L, the etching reaction time is 0.5-24 h, and the temperature is 15-40 ℃;
wherein the molecular formula of the MAB phase material is represented as MAB or M n AB 2n-2 Wherein M is selected from Mn and/or W, A is aluminum element, B is boron element, and n is 2, 3 or 4;
the molecular formula of the two-dimensional transition metal boride material is represented as MB or M n B 2n-2 Wherein M is selected from any one or the combination of two of Mn and W, B is boron, n is 2, 3 or 4, the two-dimensional transition metal boride material shows magnetic behavior at normal temperature, the space group of the MAB phase material is Cmmm, and unit cell is formed by MB or M n B 2n-2 The structure unit and the aluminum-containing atomic layer are stacked alternately.
2. The production method according to claim 1, characterized by comprising: and uniformly mixing M and/or M-containing materials, A and/or A-containing materials and B and/or B-containing materials, and reacting the obtained mixture at the high temperature of 1000-1200 ℃ for 6-12 h in an inert atmosphere to obtain the MAB phase material.
3. The production method according to claim 2, characterized in that: the M-containing material is selected from M-containing simple substance and/or M-containing alloy; and/or the material containing A is selected from simple substances containing aluminum and/or alloys containing aluminum; and/or the B-containing material is selected from boron-containing simple substance and/or boron-containing alloy.
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