CN114408873B - Etching method of MXene material - Google Patents
Etching method of MXene material Download PDFInfo
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- CN114408873B CN114408873B CN202111488980.0A CN202111488980A CN114408873B CN 114408873 B CN114408873 B CN 114408873B CN 202111488980 A CN202111488980 A CN 202111488980A CN 114408873 B CN114408873 B CN 114408873B
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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Abstract
The invention belongs to the technical field of two-dimensional nano materials, and particularly relates to an etching method of an MXene material. An etching method of MXene material includes mixing MAX phase material, chalcogen or nitrogen group elemental element powder or its related alloy phase and inorganic salt, and high-temperature reacting. The method is simple, efficient and environment-friendly, avoids a plurality of defects of preparing the MXene by using a high-toxicity and high-risk hydrofluoric acid (HF) solution as an etchant, realizes chemical modification of the surface of the MXene material, can effectively regulate and control the physical and chemical properties of the MXene material through end group modification, and is expected to further promote the functional application and large-scale preparation of the MXenes.
Description
Technical Field
The invention belongs to the technical field of two-dimensional nano materials, and particularly relates to an etching method of an MXene material.
Background
Two-dimensional (2D) transition metal carbides or carbonitrides (mxnes) are one of the latest members of the two-dimensional family of materials. MXnes is prepared by selectively etching the A layer element of a MAX phase precursor, where M represents an early transition metal element (Ti, V, nb, etc.), A is an element mainly from groups 13-16 (Al, si, etc.), and X is carbon and/or nitrogen 1. The general formula for MXenes can be written as M n+1 X n T x (n=1-3), where Tx represents a surface end group, generally considered as-F, -O or-OH. Due to its unique two-dimensional layered structure, hydrophilic surface and metallic conductivity, mxnes shows broad application prospects, in particular for electrochemical energy storage. The first report of Ti in 2011 3 C 2 After synthesis of MXene, MXenes are prepared by selectively etching the A-layer atoms in the MAX phase with an acidic aqueous solution containing fluoride ions, e.g. aqueous HF, liF+HCl mixturesAnd (3) liquid. So far, the high reactivity of the MAX phase a layer aluminum with aqueous fluoride solutions has limited the synthesis of mxnes mainly in aqueous fluoride solutions. Recently, the research team provides a novel etching method based on Lewis acid molten salt, and the preparation of the MXees material and the modification of the halogen surface end group are successfully realized. However, the major challenges of current mxnes synthesis are: (1) searching for a green harmless synthetic route; (2) Exploring a new etching route to realize the etching of MAX phase precursors with different A bits, such as Ga, in and Sn; (3) A novel MXene end group modification method was investigated.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a method for etching an MXene material, which is simple in preparation method and has universality.
In order to achieve the aim of the invention, the invention is realized by the following scheme: an etching method of MXene material includes mixing MAX phase material, chalcogen or nitrogen group elemental element powder or its related alloy phase and inorganic salt, and high-temperature reacting.
The etching method provided by the invention mainly uses chalcogen or nitrogen element and related alloy phases thereof as an etchant to realize effective etching of the A-bit element in the MAX phase precursor. At high temperature, the inorganic salt can be melted to provide a molten salt environment for etching reaction, and chalcogen or nitrogen group elemental elements and related alloys thereof are melted in the molten salt environment to generate corresponding atoms or ions with oxidability. And oxidizing the MAX phase A layer atoms by the etchant by utilizing the high oxidizing property of the etchant in the molten salt environment and the weak bonding characteristics of the MAX phase MX layer and the MAX phase A layer, thereby effectively etching the MAX phase and obtaining the MXes material. In addition, in the etching process, the surface of the MXees is terminated with the end group of the chalcogen or the nitrogen group element due to the existence of anions corresponding to the chalcogen and the nitrogen group element, so that the surface modification of the MXees material is realized. Compared with the etching method reported at present, the method is a brand new etching method, and avoids the high toxicity and high risk of hydrofluoric acid used in the past. In addition, compared with the Lewis acid molten salt etching method reported before, the method can effectively realize the end group modification of the MXees surface.
Preferably, the mol ratio of the precursor MAX phase material, chalcogen or nitrogen group elemental element powder or related alloy phase to the inorganic salt is 1: (1-3): (5-10).
Further preferably, the molar ratio of the precursor MAX phase material, chalcogen or nitrogen elemental element powder or related alloy phase to the inorganic salt is 1: (1-2): (6-8).
Preferably, the chalcogen or nitrogen group elemental element powder comprises one or more of S, se, te, P, as, sb. Further preferably, the chalcogen or nitrogen group elemental element powder is one or more of Se, te and Sb.
Preferably, the chalcogen or nitrogen group related alloy phase comprises FeS and Ag 2 S、CoS 2 、Cu 2 S、Ag 2 Se、CdSe、FeSe、NiSe、CdTe、NiTe、CoTe、FeTe、Co 2 P、Cu 3 P、Cd 3 P 2 、Cd 3 As 2 、Cu 3 As、Fe 2 As, niSb, snSb, cdSb, coSb, P-As, P-Sb, as-Sb, P-As-Sb. Further preferably, the chalcogen or nitrogen group related alloy phase is NiSe, coTe, co 2 One or more of P.
Preferably, the precursor MAX phase material comprises Ti 3 AlC 2 、Ti 2 AlC、Ti 2 AlN、Ti 4 AlN 3 、V 2 AlC、Cr 2 AlC、Nb 2 AlC、Hf 2 AlN、Ta 4 AlC 3 、Ti 3 Any one or more of AlCN.
Preferably, the inorganic salt includes any one or more of NaF, naK, liCl, naCl, KCl, naBr, KBr, KI, naI.
Preferably, the high temperature reaction temperature is 500-700 ℃ and the reaction time is 5-12h.
Preferably, the high temperature reaction is under inert gas protection.
Compared with the prior art, the method provided by the invention provides a novel MAX phase etching method for preparing the MXees two-dimensional material, and provides that alloy and chalcogen and nitrogen element simple substances with oxidability are used as etchants, so that the MAX phase is effectively etched, and in addition, in-situ modification of the MXees surface can be realized in the etching process. The preparation method is simple and efficient, is environment-friendly, and avoids various defects of using high-toxicity and high-risk hydrofluoric acid (HF) solution as an etchant to prepare the MXene. The physical and chemical properties of the MXees material can be effectively regulated and controlled by the etching method, and the method is expected to further promote the functional application and large-scale preparation of the MXees, such as promotion of the application of the MXees in the fields of catalysis, energy storage, sensing and the like.
Drawings
FIG. 1 shows an MXene material Ta having Se-containing end groups obtained in example 1 of the present invention 2 CSe crystal and precursor MAX phase Ta thereof 2 XRD pattern of AlC;
FIG. 2 shows an MXene material Ta having Se-containing end groups obtained in example 1 of the present invention 2 SEM image of CSe crystals;
FIG. 3 shows an MXene material Ta having Se-containing end groups obtained in example 1 of the present invention 2 SEM-EDS spectra of CSe crystals.
FIG. 4 is a schematic diagram of a Te-containing MXene material Nb having a terminal group obtained in example 2 of the present invention 2 CTe crystal and precursor MAX phase Nb thereof 2 XRD pattern of AlC;
FIG. 5 is a schematic diagram of a Te-containing MXene material Nb having a terminal group obtained in example 2 of the present invention 2 SEM image of CTe crystals;
FIG. 6 is a schematic diagram of a Te-containing MXene material Nb having a terminal group obtained in example 2 of the present invention 2 SEM-EDS spectra of CTe crystals.
Detailed Description
Example 1: preparation of MXene Ta 2 CSe powder
(1) Ta with granularity of 500 meshes and molar ratio of 1:1:5 is weighed 2 Grinding and mixing AlC powder, niSe powder and LiCl to obtain a mixture.
(2) The mixture was charged into an alumina crucible, and then placed into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 650 ℃, the heat preservation time is 5 hours, and the inert atmosphere is protected. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.
(3) Deionized water and wineAnd (3) finely washing the reaction product: the reaction product was placed in a beaker, deionized water was added, and after stirring and ultrasonic cleaning for 30 minutes, the remaining salt in the reaction product was washed away, followed by suction filtration. And (3) placing the reaction product obtained by suction filtration into a baking oven at 40 ℃, and taking out after 12 hours to obtain a powder product. FIG. 1 shows the reaction product Ta of this example 2 CSe and precursor MAX phase Ta thereof 2 XRD results of AlC. Ta compared with the precursor MAX 2 The diffraction peak of CSe broadens or even disappears, while the (002) plane characteristic peak shifts to a low angle, indicating that the a-site Al atom is etched while the formation of Se end groups causes the (002) crystal plane to expand along the c-axis. Ta was determined using Scanning Electron Microscopy (SEM) 2 Topographical features of CSe, as shown in fig. 2. The Energy Dispersive Spectroscopy (EDS) results confirm the presence of Se element signals, while Al element signals are significantly attenuated or even vanished, which also indicates etching of a-site Al atoms and formation of Se end groups, and also that there is a small amount of O element in the product, which is introduced during the product washing process, as shown in fig. 3.
Example 2: preparation of MXene Nb 2 CTe powder
(1) Nb with the granularity of 500 meshes and the molar ratio of 1:1:6:6 is weighed 2 Grinding and mixing AlC powder, te powder, naCl and KCl to obtain a mixture.
(2) The mixture was charged into an alumina crucible, and then placed into a high-temperature vacuum tube furnace for reaction. The reaction conditions are as follows: the reaction temperature is 700 ℃, the heat preservation time is 12 hours, and the inert atmosphere is protected. And after the sintering temperature is reduced to room temperature, taking out the reaction product in the alumina crucible.
(3) Washing the reaction product with deionized water and alcohol: the reaction product was placed in a beaker, deionized water was added, and after stirring and ultrasonic cleaning for 30 minutes, the remaining salt in the reaction product was washed away, followed by suction filtration. And (3) placing the reaction product obtained by suction filtration into a baking oven at 40 ℃, and taking out after 12 hours to obtain a powder product.
As shown in FIG. 4, nb 2 CTe the characteristic peak of the MAX phase of the precursor was significantly reduced and the same (004) plane characteristic peak as that of the previous experimental results could be observed, indicating that there was a conversion of the MAX phase to MXene material during the reaction.In addition, the particle morphology and elemental composition of the reaction product were analyzed by scanning electron microscopy and EDS spectroscopy, the morphology being shown in fig. 5. The energy spectrum result in fig. 6 shows that the Al element signal is obviously weakened, meanwhile, a stronger Te element signal appears, and the combination of the XRD result can judge that the Te element effectively etches the MAX phase A element, and the MXene with the Te end group is generated.
The above description of the embodiments of the invention is not intended to limit the invention, but rather, it is to be understood that the invention is capable of numerous modifications and variations in accordance with the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The etching method of the MXene material is characterized by comprising the steps of mixing a precursor MAX phase material, chalcogen or nitrogen group elemental element powder or related alloy phase thereof and inorganic salt, and reacting at high temperature; the chalcogen or nitrogen group elemental element powder comprises one or more of S, se, te, P, as, sb; the chalcogen or nitrogen group corresponding alloy phase comprises FeS and Ag 2 S、CoS 2 、Cu 2 S、Ag 2 Se、CdSe、FeSe、NiSe、CdTe、NiTe、CoTe、FeTe、Co 2 P、Cu 3 P、Cd 3 P 2 、Cd 3 As 2 、Cu 3 As、Fe 2 As, niSb, snSb, cdSb, coSb, P-As, P-Sb, as-Sb, P-As-Sb; the precursor MAX phase material comprises Ti 3 AlC 2 、Ti 2 AlC、Ti 2 AlN、Ti 4 AlN 3 、V 2 AlC、Cr 2 AlC、Nb 2 AlC、Hf 2 AlN、Ta 4 AlC 3 、Ti 3 Any one or more of AlCN; the inorganic salt comprises any one or more of NaF, naK, liCl, naCl, KCl, naBr, KBr, KI, naI.
2. The method for etching an MXene material according to claim 1, characterized in that the molar ratio of the precursor MAX phase material, chalcogen or nitrogen group elemental element powder or its related alloy phase to the inorganic salt is 1: (1-3): (5-10).
3. The method for etching an MXene material according to claim 1, wherein the high temperature reaction is carried out at 500-700 ℃ for 5-12 hours.
4. A method of etching an MXene material according to claim 1 or 3, characterized in that the high temperature reaction is under the protection of inert gas.
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| CN115845886B (en) * | 2022-11-20 | 2024-02-23 | 复旦大学 | CdSe/MXene composite photocatalyst and preparation method and application thereof |
| CN116161661A (en) * | 2023-03-07 | 2023-05-26 | 天津大学 | Method for preparing MXene two-dimensional material by gas phase etching MAX phase and application |
| CN116354348A (en) * | 2023-03-24 | 2023-06-30 | 哈尔滨工程大学 | MAX phase etching method based on novel metal salt eutectic solvent |
| CN117241661B (en) * | 2023-11-10 | 2024-03-15 | 北京科技大学 | Two-dimensional oxygen group element end group MXene film, preparation method thereof and brain-like semiconductor device |
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