CN114180969A - Preparation method and application of novel nitrogen-containing MAX phase material and two-dimensional material - Google Patents

Preparation method and application of novel nitrogen-containing MAX phase material and two-dimensional material Download PDF

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CN114180969A
CN114180969A CN202210053434.2A CN202210053434A CN114180969A CN 114180969 A CN114180969 A CN 114180969A CN 202210053434 A CN202210053434 A CN 202210053434A CN 114180969 A CN114180969 A CN 114180969A
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nitrogen
max phase
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CN114180969B (en
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杨树斌
杜志国
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Beihang University
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Abstract

The invention discloses a preparation method and application of a novel nitrogen-containing MAX phase material and a two-dimensional material, wherein the preparation method of the novel nitrogen-containing MAX phase material comprises the following steps: the nitrogen-containing MAX phase material is prepared by taking nitride of A, simple substance or compound of more than four transition metals and simple substance or compound of A as raw materials for reaction, or taking nitride of A, simple substance or compound of at least one transition metal and nitrogen-free M 'AX phase material as raw materials for reaction, wherein the types of the transition metals and the elements in M' are more than four. The preparation method provided by the invention is simple in process, low in cost and easy for industrial amplification production, and lays a foundation for application of nitrogen-containing medium-entropy or high-entropy MAX phase materials and two-dimensional materials.

Description

Preparation method and application of novel nitrogen-containing MAX phase material and two-dimensional material
The present application claims the priority of the chinese patent application with the application number of 202110560245.X entitled "preparation method and use of novel nitrogen-containing MAX phase material and two-dimensional material" filed from chinese patent office at 21/5/2021, the contents of which are incorporated herein by reference.
Technical Field
The invention relates to the field of new materials, in particular to a preparation method and application of a novel nitrogen-containing MAX phase material and a two-dimensional material.
Background
The layered transition metal carbides, nitrides and carbonitrides (MAX phases) have a rich chemical composition, of the formula Mn+1AXnM represents an early transition metal element such as Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, etc., A is mainly a group 13-16 element such as Al, Si, P, S, etc., and X represents a C and/or N element. The MAX phase material is also called a conductive ceramic because the strong coupling between the 3d orbital of the M metal atom and the 2p orbital of the a atom imparts electrical conductivity to the MAX phase metal and thermal conductivity to the ceramic. To date, over 150 species of MAX phase materials have been discovered, but the nitrogen-containing MAX phase is concentrated only in Ti2AlN、Ti2AlCxN1-x、Ti3AlCN and Ti4AlN3Very few, nitrogen-containing, high entropy MAX phases (containing at least 5 transition metal elements) have not been reported to date. Accordingly, a high-entropy two-dimensional material containing nitrogen is still not obtained. The reported nitrogen-containing high-entropy materials mainly focus on rock salt structure (Cr)0.2Mo0.2Nb0.2V0.2Zr0.2) N and (V)0.2Nb0.2Ta0.2Mo0.2W0.2) N and the like, and has a three-dimensional block structure, and the high-entropy nitride has excellent mechanical, magnetic, high-temperature-resistant and corrosion-resistant properties. Therefore, it can be presumed that,the nitrogen-containing high-entropy two-dimensional material tends to show more excellent physicochemical properties. Therefore, the development of a nitrogen-containing high-entropy two-dimensional material, a nitrogen-containing high-entropy MAX-phase material and a preparation method thereof are urgently needed.
Currently, the common method for preparing MAX phase materials in the prior art is a high temperature sintering process comprising the steps of: (1) mixing elementary substance powder forming MAX phase according to a proportion; (2) putting the powder mixture into an agate ball milling tank, and ball milling for a plurality of hours by using a ball mill; (3) and putting the mixed powder subjected to ball milling into an alumina crucible, and placing the alumina crucible into a tubular furnace for high-temperature sintering under the protection of argon. (4) And after the reaction is finished, cooling to room temperature, taking out the sample, grinding and sieving to obtain MAX phase powder. However, when the method is used for preparing the nitrogen-containing medium-entropy or high-entropy MAX phase material, because four or more transition metal simple substances are required to be added, the transition metal simple substances are easy to react with the nitrogen-containing raw material under a high-temperature environment to generate transition metal nitride particles with a rock salt structure, and the homogeneous medium-entropy or high-entropy MAX phase material cannot be prepared.
Disclosure of Invention
The invention provides a preparation method of a novel nitrogen-containing MAX phase material, aiming at the technical problem that a high-temperature sintering method in the prior art is difficult to prepare a homogeneous nitrogen-containing medium-entropy or high-entropy MAX phase material, and the preparation method comprises the following steps: the method comprises the following steps of (1) reacting nitride containing A, more than four transition metal simple substances or compounds and the simple substance A or compound serving as raw materials to prepare a novel nitrogen-containing MAX phase material; wherein A is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements; or, taking nitride containing A, at least one transition metal simple substance or compound and nitrogen-free M' AX phase material as raw materials to react to prepare the novel nitrogen-containing MAX phase material; wherein, the types of the elements in the transition metal and the M' are more than four, and A is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements;
in some embodiments, the raw material further comprises a simple substance X, wherein X is carbon or boron; and/or the types of transition metal elements in the raw materials are four, five or six; and/or the compound of the transition metal is carbide.
In some embodiments, the transition metal and/or M' are each selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pt, Au, Ag, Pd, Cu, or Bi elements; preferably, the transition metal contains Ti element; and/or A is selected from Al, Si, P, S, Fe, Cu, Zn, Ga, Ge, As, Cd, In, Sn, Tl, Pb or Bi elements; and/or X in the obtained novel nitrogen-containing MAX phase material is carbon and nitrogen elements.
In some embodiments, prior to performing the reaction, further comprising: grinding: grinding the raw materials; and/or, a pressing step: pressing the raw materials to form the composite material; preferably, the pressurization pressure is between 10MPa and 50 MPa.
In some embodiments, the temperature of the reaction is between 600 ℃ to 3000 ℃; preferably, between 1000 ℃ and 1700 ℃; and/or the reaction time is between 1h and 20 h.
In some embodiments, the novel nitrogen-containing MAX phase material is prepared such that the atomic ratio C: N is (1-x): x, wherein (0< x < 1);
the invention also provides a preparation method of the nitrogen-containing two-dimensional material, which comprises the following steps: and reacting the novel nitrogen-containing MAX phase material prepared by the preparation method with an etching agent to etch the component A to obtain the nitrogen-containing two-dimensional material.
In some embodiments, the etchant is one or more of a simple halogen, a halogen hydride, or a nitrogen hydride; or the etchant is a hydrogen halide solution, an acid solution and a halide salt system or a halogen metal salt.
In some embodiments, the reaction is a vapor phase etch, the etchant is in the vapor phase, or is capable of being converted to the vapor phase for etching; and/or the thickness of the obtained sheet layer of the nitrogen-containing two-dimensional material is between 2nm and 10 nm.
The invention also discloses an application of the nitrogen-containing high-entropy AMX phase material or the nitrogen-containing two-dimensional material obtained by the preparation method in catalysis, sensors, electronic devices, super capacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials or supercapacitors.
The method has the beneficial technical effects that the nitride of A is used as a reaction raw material and reacts with the transition metal element to produce the nitrogen-containing MAX phase material, the produced nitrogen-containing MAX phase material can be used as a framework material to provide a matrix in which other transition metal elements are diffused, or the nitrogen-containing high-entropy MAX phase material is obtained through isomorphous replacement reaction among the MAX phase materials. The novel nitrogen-containing high-entropy MAX phase material is prepared based on the invention, the etching agent is used for etching A in the material, and a novel nitrogen-containing medium-entropy or high-entropy two-dimensional material (nitrogen-containing MXene material) is obtained, so that a new variety is added to a two-dimensional material family. The preparation method disclosed by the invention is simple in process, low in cost and easy for industrial amplification production, lays a foundation for the application of the nitrogen-containing medium-entropy or high-entropy MAX phase material and the nitrogen-containing medium-entropy or high-entropy two-dimensional material, and has a wide application prospect in the fields of catalysis, sensors, electronic devices, super capacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials, superconducting materials and the like in the future.
Drawings
FIG. 1 Nitrogen-containing high entropy MAX phase Material (Ti) in example 1 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5SEM photograph of (a).
FIG. 2 shows a nitrogen-containing high-entropy MAX phase material (Ti) in example 1 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5XRD spectrum of (1).
FIG. 3A nitrogen-containing high-entropy MAX-phase material (Ti) in example 2 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5SEM photograph of (a).
FIG. 4 shows a nitrogen-containing high-entropy MAX phase material (Ti) in example 2 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5XRD spectrum of (1).
FIG. 5A nitrogen-containing high-entropy two-dimensional material (Ti) in example 3 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxSEM photograph of (a).
FIG. 6A nitrogen-containing high-entropy two-dimensional phase material (Ti) in example 3 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxXRD spectrum of (1).
FIG. 7A nitrogen-containing high-entropy two-dimensional material (Ti) in example 3 of the present invention0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxHRTEM and STEM photographs and protoxin profiles.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The technical solution of the present invention will be described below by way of specific examples. It is to be understood that one or more of the steps mentioned in the present invention does not exclude the presence of other methods or steps before or after the combined steps, or that other methods or steps may be inserted between the explicitly mentioned steps. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method well known to those skilled in the art.
The technical concept of the invention is that at least one transition metal simple substance or carbide reacts with nitride of A to generate a nitrogen-containing MAX phase material, then the nitrogen-containing MAX phase material is taken as a framework, and a plurality of transition metal elements are diffused and doped into the framework to prepare the nitrogen-containing MAX phase material (medium-entropy or high-entropy MAX phase material), and the technical scheme has two implementation modes:
the nitrogen-containing medium-entropy or high-entropy MAX phase material is prepared by taking nitride of A, simple substances or compounds of more than four transition metals and simple substances or compounds of A as raw materials for reaction, wherein A is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements. The mechanism of the reaction is explained as follows: reacting the nitride of the A with a simple substance or a carbide of a transition metal to generate a nitrogen-containing MAX phase material, and then taking the nitrogen-containing MAX phase material as a framework, wherein the residual transition metal element in the simple substance or the carbide of the transition metal permeates into the nitrogen-containing MAX phase material under the condition of high temperature to obtain the nitrogen-containing high-entropy MAX phase material; or reacting the nitride of the A with simple substances or carbides of a plurality of transition metals to generate a plurality of nitrogen-containing MAX phase materials, and carrying out isomorphous displacement reaction on the plurality of nitrogen-containing MAX phase materials under the high-temperature condition to obtain the homogeneous nitrogen-containing high-entropy MAX phase material. In the technical scheme, the nitride of the raw material A and the simple substance or the carbide of the transition metal belong to industrial products, the preparation is easy, the cost is low, the nitrogen-containing high-entropy MAX phase material can be prepared by a high-temperature one-step method, and the industrial practical value is achieved.
And (II) reacting the nitride of A, at least one simple substance or carbide of transition metal element and at least one M ' AX phase material, wherein the types of the transition metal element and the M ' in the M ' AX phase in the raw materials are more than five, and A is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements. The mechanism of the reaction is explained as follows: and reacting the nitride of the A with a simple substance or carbide of a transition metal element to generate a nitrogen-containing MAX phase material, taking the nitrogen-containing MAX phase material as a framework, carrying out isomorphous replacement reaction on the nitrogen-containing MAX phase material and an M 'AX phase under a high temperature condition, and diffusing the M' into the framework of the nitrogen-containing MAX phase material to obtain the nitrogen-containing high-entropy MAX phase material. In the technical scheme, the medium-entropy or high-entropy MAX phase material containing nitrogen can be prepared by utilizing isomorphous replacement reaction of the MAX phase material.
Referring to the definition of various metal alloy elements in the material science, in the application, when M is four metal elements in the prepared novel nitrogen-containing MAX phase material, the material is called as a medium-entropy MAX phase material, and when M is more than five metal elements, the material is called as a high-entropy MAX phase material.
The nitrogen-containing medium-entropy or high-entropy MAX phase material prepared by the method belongs to one type of MAX phase material large family, and the preparation method can also obtain a series of novel medium-entropy or high-entropy MAX phase materials.
The novel nitrogen-containing MAX phase material prepared by the invention consists of M element, A element and X element, and the chemical general formula of the material is Mn+1AXnWherein, the M element is at least four metal elements in IIIB, IVB, VB, VIB, VIIB, VIII, IB and IIB groups, the A element is at least one of at least one group element in VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA groups, and the X element is nitrogen element and at least one non-metal element in IIIA, IVA, VA and VIA; n is 1, 2, 3, 4, 5 or 6.
In some embodiments, the X element is carbon and nitrogen; the M element is selected from more than four of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pt, Au, Ag, Pd, Cu or Bi; the element A is at least one element selected from the group consisting of Al, Si, P, S, Fe, Cu, Zn, Ga, Ge, As, Cd, In, Sn, Tl, Pb and Bi.
In some embodiments, the number of element types of the M element in the novel nitrogen-containing MAX phase material prepared as described above is four, five or six.
The novel nitrogenous two-dimensional material prepared by the invention is obtained by etching the element A in the novel nitrogenous MAX phase material.
Example 1
The invention provides a method for preparing nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The preparation method comprises the following steps:
the material preparation step: according to the formula of the high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The medium stoichiometric ratio (molar ratio) of Ti, Nb, Ta, V, Zr, AlN, Al and graphite is used as raw material precursors, the molar ratio of Ti to Nb to Ta to V to Zr to AlN to C is 0.4:0.4:0.4:1:0.2:1, and each raw material precursor is accurately weighed according to the corresponding molar ratio;
grinding: putting the raw materials into a ball milling tank for ball milling, wherein the ball milling rotation speed is 600rpm, the ball milling time is 20 hours, and after the ball milling is finished, putting the mixed powder into a powder tabletting mold for cold pressing treatment, wherein the pressure is 20MPa, and the pressurizing time is 5 minutes;
sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at the speed of 5 ℃/min under the Ar atmosphere, preserving heat for 1h, cooling along with the furnace, taking out the block obtained after cooling, and grinding to obtain the nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5And (3) powder.
For nitrogen-containing high-entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Scanning Electron Microscope (SEM) testing was performed, and the results are shown in FIG. 1, (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Has an irregular three-dimensional block structure, similar to the shape of the MAX phase prepared by most. For nitrogen-containing high-entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The X-ray diffraction (XRD) analysis showed that the raw material (Ti) was as shown in FIG. 20.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Strong diffraction peaks appear in the middle XRD pattern,and the (002) peak appears at the position of 12.9 degrees, which shows that the material has a layered structure and is a synthesized nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Diffraction pattern of (A) and reported quaternary MAX phase Ti2AlC0.5N0.5Consistent with no other impurity peaks of carbides and nitrides, indicating the resulting nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Is a single phase of high purity.
Example 2
The invention provides a method for preparing nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The preparation method comprises the following steps:
the material preparation step: according to the chemical formula (Ti) of the nitrogen-containing high-entropy MAX phase0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The medium stoichiometric ratio (molar ratio) of (1) adopts Ti, Nb, Ta, V, Zr, TiC, NbC, TaC, VC, ZrC, AlN and Al as raw material precursors, the molar ratio of Ti to Nb to Ta to V to Zr to TiCto NbC to TaC to VC to ZrC to AlN to Al is 0.3:0.3:0.3:0.1:0.1:0.1: 0.5:0.7, and each raw material precursor is accurately weighed according to the corresponding molar ratio;
grinding: putting the raw materials into a ball milling tank for ball milling, wherein the ball milling rotation speed is 600rpm, the ball milling time is 20 hours, and after the ball milling is finished, putting the mixed powder into a powder tabletting mold for cold pressing treatment, wherein the pressure is 20MPa, and the pressurizing time is 5 minutes;
sintering: transferring the ball-milled block into a corundum crucible, heating to 1500 ℃ at the speed of 5 ℃/min under the Ar atmosphere, preserving heat for 1h, cooling along with the furnace, taking out the block obtained after cooling, and grinding to obtain the nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5And (3) powder.
For nitrogen-containing high-entropy MAX phaseMaterial (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Scanning Electron Microscope (SEM) testing was performed, and the results are shown in FIG. 3, (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Has an irregular three-dimensional block structure, similar to the shape of the MAX phase prepared by most. For nitrogen-containing high-entropy MAX phase material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The X-ray diffraction (XRD) analysis showed that the raw material (Ti) was as shown in FIG. 40.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5A strong diffraction peak appears in a middle XRD pattern, and a (002) peak appears at a position of 12.9 degrees, which shows that the material has a layered structure, and a synthesized nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Diffraction pattern of (A) and reported quaternary MAX phase Ti2AlC0.5N0.5Consistent with no other impurity peaks of carbides and nitrides, indicating the resulting nitrogen-containing high-entropy MAX phase (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Is a single phase of high purity.
Example 3
This example provides a specific example of a vapor phase method for etching nitrogen-containing high-entropy MAX to prepare a high-entropy two-dimensional material, and uses the nitrogen-containing high-entropy MAX phase (Ti) prepared in example 10.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The method is characterized in that commercial liquefied HCl gas is used as an etching agent to react to prepare a two-dimensional material as a precursor, and a selected reactor is a tubular furnace and comprises the following steps:
1) placing powdered (Ti) in the tube furnace0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5；
2) Introducing HI gas into the tubular furnace for a period of time, and sealing the reaction cavity after the reaction cavity in the reaction device is filled with the HI gas;
3) heating the interior of the reaction device to 700 ℃, preserving heat for 30min, and carrying out etching reaction to obtain a target product high-entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5Tx。
And after the reaction device is naturally cooled to the room temperature, taking out the target product. To (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5High entropy two dimensional material (Ti) after reaction with HCl0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxSEM tests are carried out on the two target products, the results are shown in figure 5, the target product after reaction is in an accordion layered structure, the accordion structure is formed by stacking ultrathin two-dimensional nanosheets layer by layer, and the target product is obviously different from a raw material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The lamellar bulk morphology (FIG. 1). To (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5And nitrogen-containing high-entropy MXene (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxXRD analysis was carried out, and the results are shown in FIG. 6, by comparison, starting material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5The (002) peak in (III) appeared at the 12.9 ℃ position, while the (002) peak in the target product after reaction with HI gas was shifted to a low angle of 7.2 ℃, indicating that HI gas was etched in the gas phase reaction (Ti0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5Al element in the medium to generate a high-entropy two-dimensional material (Ti) with a lamellar structure0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxThis leads to an enlargement of the layer spacing, which is consistent with the scanning electron micrograph results. High entropy two-dimensional material (Ti) of target product0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxThe STEM photograph of (A) has a large number of two-dimensional ultrathin nanosheets, as shown in FIG. 7, indicating that the nanosheets are accordion-like (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxA large number of two-dimensional nanosheets with good single crystal structures can be obtained by simple peeling, and the high-entropy two-dimensional material (Ti) prepared by the atomic force microscope AFM test0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5TxThe thickness of (A) is between 2nm and 3 nm.
Example 4
The embodiment provides another method for preparing a nitrogen-containing high-entropy two-dimensional material, and the nitrogen-containing high-entropy MAX-phase material prepared in the embodiment 1 comprises the following steps:
taking 50ml of 48 percent hydrofluoric acid (HF) as an etching agent, taking 1g of the nitrogen-containing high-entropy MAX phase obtained in the step (1) in the embodiment 1, placing the nitrogen-containing high-entropy MAX phase in the etching agent, reacting for 48 hours at 50 ℃, and after the reaction is finished, performing centrifugal separation, water washing and drying treatment to obtain the nitrogen-containing high-entropy two-dimensional material (Ti)0.2Nb0.2Ta0.2Zr0.2V0.2)2C0.5N0.5T (wherein T)xRepresents a functional group contained).
In some embodiments, the etchant may also be selected from one or more of a simple halogen, a halogen hydride, or a nitrogen hydride, such as: br2、I2、HBr、NH3Or pH3And the like. In the etching process, the gas-phase etchant can enter into the etched MAX phase gaps to more fully etch the phase A, so that the high-entropy two-dimensional material sheet layer (2 nm-10 nm) with the ultrathin structure is obtained. In addition, the gas phase etching does not contain solid impurities,The powder material of the high-entropy two-dimensional lamellar can be directly obtained, complex processes such as purification and drying of liquid phase etching are avoided, the industrial batch preparation can be realized, the preparation cost of the high-entropy two-dimensional lamellar material can be reduced, and the method has great commercial value.
In some embodiments, prior art liquid phase etchants may also be employed, including: a hydrogen halide solution, an acid solution + halide salt system, or a halide metal salt.
Example 5
This example provides an alternative preparation of a nitrogenous mid-entropy MAX phase (Ti)0.25Nb0.25Ta0.25V0.25)2AlC0.75N0.25The preparation method comprises the following steps:
the material preparation step: according to the chemical formula (Ti) of the nitrogen-containing high-entropy MAX phase0.2Nb0.2Ta0.2Zr0.2V0.2)2AlC0.5N0.5In the medium stoichiometric ratio (molar ratio) of (A) is Ti, AlN, Nb2AlC、Ta2AlC、V2AlC is used as a raw material precursor, and the molar ratio of Ti to AlN to Nb is2AlC:Ta2AlC:V2AlC＝2:1:1:1:1；
Grinding: putting the raw materials into a ball milling tank for ball milling, wherein the ball milling rotation speed is 600rpm, the ball milling time is 20 hours, and after the ball milling is finished, putting the mixed powder into a powder tabletting mold for cold pressing treatment, wherein the pressure is 20MPa, and the pressurizing time is 5 minutes;
sintering: transferring the ball-milled block into a corundum crucible, heating to 1200 ℃ at the speed of 5 ℃/min under the Ar atmosphere, preserving heat for 1h, cooling along with the furnace, taking out the cooled block, and grinding to obtain the nitrogen-containing intermediate entropy MAX phase (Ti)0.25Nb0.25Ta0.25V0.25)2AlC0.75N0.25And (3) powder.
In the preparation method of the invention, the simple substance of the transition metal is preferably selected as the raw material, and more preferably, the simple substance of the transition metal contains a metal Ti element, wherein the metal Ti element can react with the nitride A at a relatively low temperature (1200-1400 ℃) to generate the nitrogen-containing MAX phase material, and the nitrogen-containing MAX phase material is taken as a framework to diffuse other transition metal elements therein, so as to obtain the nitrogen-containing MAX phase material with medium entropy or high entropy.
Example 6
The embodiment provides another preparation method of a nitrogen-containing high-entropy MAX phase, which comprises the following steps:
the material preparation step: according to the formula of the high-entropy MAX phase (Ti)1/6Nb1/6Ta1/6Zr1/6V1/6Hf1/6)2AlC0.5N0.5In the (molar ratio) of Ti, AlN, HfC, V, Al, (Nb)1/3Ta1/3Zr1/3)2AlC is used as a raw material precursor, and the molar ratio of Ti to AlN to Hf to V to Al to Nb1/3Ta1/3Zr1/3)2Accurately weighing each raw material precursor according to AlC ratio of 1.3:2:1.3:1.3:1.3: 2;
grinding: putting the raw materials into a mortar for manual grinding for 10min, and after grinding, putting the mixed powder into a powder tabletting mold for cold pressing treatment under the pressure of 20MPa for 5 min;
sintering: transferring the ball-milled block into a corundum crucible, heating to 1400 ℃ at a speed of 5 ℃/min under Ar atmosphere, preserving heat for 1h, heating to 1800 ℃ and preserving heat for 1h, cooling along with the furnace, taking out the block obtained after cooling, and grinding to obtain the nitrogen-containing high-entropy MAX phase (Ti1/6Nb1/6Ta1/6Zr1/6V1/6Hf1/6)2AlC0.5N0.5And (3) powder.
It should be noted that, in the high-temperature sintering process of the present invention, a complex reaction occurs, the heating temperature may be within 1000 ℃ to 3000 ℃, the optimal conditions of different types of MAX phase materials are determined through limited experiments, and an optimized process may also be obtained, for example, the reaction is controlled by a step-wise heating manner.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. A method for preparing a novel nitrogen-containing MAX phase material is characterized by comprising the following steps:
the method comprises the following steps of (1) reacting nitride containing A, more than four transition metal simple substances or compounds and the simple substance A or compound serving as raw materials to prepare a novel nitrogen-containing MAX phase material; wherein A is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements;
or, taking nitride containing A, at least one transition metal simple substance or compound and nitrogen-free M' AX phase material as raw materials to react to prepare the novel nitrogen-containing MAX phase material; wherein, the types of the elements in the transition metal and the M' are more than four, and the A is selected from at least one of VIIB, VIII, IB, IIB, IIIA, IVA, VA and VIA group elements.
2. The method according to claim 1, wherein the raw material further comprises a simple substance X, wherein X is carbon or boron;
and/or the types of transition metal elements in the raw materials are four, five or six;
and/or the compound of the transition metal is carbide.
3. The production method according to claim 1 or 2, wherein the transition metal or the M' is selected from elements of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Co, Ni, Pt, Au, Ag, Pd, Cu, or Bi; preferably, the transition metal contains Ti element;
and/or A is selected from Al, Si, P, S, Fe, Cu, Zn, Ga, Ge, As, Cd, In, Sn, Tl, Pb or Bi elements;
and/or X in the obtained novel nitrogen-containing MAX phase material is carbon and nitrogen elements.
4. The method of claim 1, further comprising, prior to performing the reaction:
grinding: grinding the raw materials;
and/or, a pressing step: pressing the raw materials to form the composite material; preferably, the pressurization pressure is between 10MPa and 50 MPa.
5. The method of claim 1, wherein the reaction temperature is between 600 ℃ and 3000 ℃; preferably, between 1000 ℃ and 1700 ℃;
and/or the reaction time is between 1h and 20 h.
6. The method of claim 3, wherein the novel nitrogen containing MAX phase material is produced with an atomic ratio C: N of (1-x): x, where (0< x < 1).
7. A preparation method of a nitrogen-containing two-dimensional material is characterized by comprising the following steps:
reacting the novel nitrogen-containing MAX phase material prepared by the preparation method of any one of claims 1 to 6 with an etching agent to etch component A therein to obtain the nitrogen-containing two-dimensional material.
8. The method of claim 7, wherein the etchant is one or more of a halogen element, a halogen hydride, or a nitrogen hydride;
or the etchant is a hydrogen halide solution, an acid solution and a halide salt system or a halogen metal salt.
9. The method according to claim 7, wherein the reaction is a vapor phase etching, and the etchant is a vapor phase or can be converted to a vapor phase for etching;
and/or the thickness of the obtained sheet layer of the nitrogen-containing two-dimensional material is between 2nm and 10 nm.
10. Use of the nitrogen-containing high-entropy AMX phase material obtained by the preparation method according to any one of claims 1 to 6 or the nitrogen-containing two-dimensional material obtained by the preparation method according to any one of claims 7 to 9 in catalysis, sensors, electronic devices, supercapacitors, batteries, electromagnetic shielding, wave-absorbing materials, corrosion-resistant materials or ultracapacitors.
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