CN112850710B - Method for preparing single-layer Mxene nanosheet by using steam stripping technology - Google Patents

Method for preparing single-layer Mxene nanosheet by using steam stripping technology Download PDF

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CN112850710B
CN112850710B CN202110097387.7A CN202110097387A CN112850710B CN 112850710 B CN112850710 B CN 112850710B CN 202110097387 A CN202110097387 A CN 202110097387A CN 112850710 B CN112850710 B CN 112850710B
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mxene
mxene nanosheet
layer mxene
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CN112850710A (en
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苏忠
赖超
曲婕
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Jiangsu Normal University
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    • C—CHEMISTRY; METALLURGY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

Abstract

The invention discloses a method for preparing a single-layer Mxene nanosheet by using a steam stripping technology, which comprises the steps of dispersing etched MAX phase materials into a certain amount of solvent to obtain a mixed solution, heating the mixed solution to boiling, continuously adding the solvent along with the evaporation of the solvent in the heating process to maintain the volume unchanged, keeping the boiling for 1-2 h, stopping heating, cooling to room temperature, and then freezing, drying and drying to obtain the single-layer Mxene nanosheet. The method adopts steam molecules as stripping agents to realize the high-efficiency stripping of MXene blocks; the used solvent has wide source, easy obtaining and low cost, thereby greatly reducing the preparation cost of the single-layer Mxene nanosheet; the method has mild reaction conditions, simple operation and environmental friendliness, the yield is close to 100 percent, and the method is favorable for large-scale production; the single-layer Mxene nanosheet prepared by the method has a good application prospect in the fields of energy storage, lubrication, adsorption, catalysts and the like.

Description

Method for preparing single-layer Mxene nanosheet by using steam stripping technology
Technical Field
The invention relates to the technical field of Mxene material preparation, in particular to a method for preparing a single-layer Mxene nanosheet by utilizing a steam stripping technology.
Background
Since 2011, two-dimensional transition metal carbide or carbonitride (MXene) is widely applied to the fields of water purification adsorption, energy storage, photocatalysis, hydrogen storage and the like by virtue of a unique lamellar structure, excellent conductivity and hydrophilic surface, and good flexibility and compressive strength. The MAX phase is a ternary compound with a microscopic layered structure and the molecular formula is Mn+1AXnWherein M layer is a group III B, IV B, V B, VI B early transition metal element, A layer is mainly a group IIIA, IV A element, X layer is carbon or nitrogen, n is 1-3, the MAX phase material which has been researched and synthesized up to now has about 70 kinds, wherein Ti is3SiC2The most extensive studies.
MXene is currently prepared mainly by selective etching of the a layer elements (Al, Si, etc.) in the MAX phase. Common etching methods are acid etching (hydrofluoric acid or corresponding fluoride), alkali etching and high temperature molten salt method. And stacking the etched MXene together, and stripping the MXene to obtain the single-layer MXene nanosheet.
The commonly used stripping method is an ultrasonic stripping method, namely small molecules of a solvent enter between MXene sheets, the interlayer distance is increased, the van der Waals force between the sheets is reduced, and the MXene is stripped in the subsequent ultrasonic oscillation process. Common stripping agents comprise water, ethanol, dimethyl sulfoxide, dimethylformamide, tetrabutylammonium hydroxide and the like, and small molecular agents with good wettability can better enter between etched MXene sheets, so that massive MXene can be stripped in the ultrasonic oscillation process. However, the ultrasonic oscillation method has the problems of long preparation period, high energy consumption, low monolithic layer yield (10-20%) and the like, so that the MXene two-dimensional nano material is expensive and cannot realize large-scale production.
Disclosure of Invention
The invention aims to provide a method for preparing a single-layer Mxene nanosheet by using a steam stripping technology, which can shorten the preparation period, reduce the preparation energy consumption and improve the yield of single-layer layers, thereby reducing the manufacturing cost of an MXene two-dimensional nanomaterial and further realizing large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing a single-layer Mxene nanosheet by using a steam stripping technology comprises the following steps:
(1) dispersing the etched MAX phase material in a container with scales and a certain amount of solvent to obtain a mixed solution,
(2) and heating the mixed solution to boiling, continuously adding the solvent into the mixed solution along with the evaporation of the solvent in the heating process to maintain the scale of the solvent in the container unchanged, namely maintaining the volume of the solvent unchanged in the evaporation process, after boiling for 1-2 h, stopping heating, cooling to room temperature, and freeze-drying to obtain the single-layer Mxene nanosheet.
Preferably, in step (1), the mass ratio of MAX phase material to solvent is 1: (20-30).
Preferably, the solvent is one or more of water, ethanol, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide and tetrabutylammonium hydroxide.
Preferably, in the MAX phase material, the M layer comprises one or more elements of Ti, Zr, Hf, V, Nb, Ta, Cr and Sc; the A layer is Al or Si; the X layer is C or N element.
Preferably, MAX phase materialsIs Ti2AlC or Ti3SiC2。
Preferably, the thickness of the single-layer Mxene nanosheet prepared by the method is 1.5-100 nm.
Compared with the prior art, the invention has the following advantages:
(1) according to the method, steam molecules are used as a stripping reagent, because gaps exist among MAX phase material sheet layers, solvent small molecules can permeate into the sheet layers, the volume of the solvent molecules is slowly expanded along with the heating to become steam molecules, the steam molecules can expand the sheet layers in the heating overflow process to increase the layer spacing and destroy van der Waals force among the sheet layers, so that the MXene block is efficiently stripped, and the preparation period is further shortened;
(2) the solvent used in the invention has wide source, easy obtaining and low cost, thereby greatly reducing the preparation cost of the single-layer Mxene nanosheet;
(3) the method has the advantages of mild reaction conditions, simple operation, environmental friendliness, low preparation energy consumption, and nearly 100% yield of single layers, and is beneficial to large-scale production;
(4) the single-layer Mxene nanosheet prepared by the method has adjustable and controllable electrical properties, dielectric properties and the like, and has good application prospects in the fields of energy storage, lubrication, adsorption, catalysts and the like.
Drawings
Fig. 1 is SEM images of MXene precipitate (a) and monolayer MXene two-dimensional nanoplatelets (b) obtained after exfoliation in comparative example one and example one;
fig. 2 is an X-ray diffraction spectrum of the MXene precipitate (a) and the monolayer MXene two-dimensional nanosheet (b) obtained after the stripping of the comparative example one and the example one;
fig. 3 is SEM images of MXene precipitate (a) and monolayer MXene two-dimensional nanoplatelets (b) obtained after exfoliation in comparative example two and example two;
fig. 4 is SEM images of MXene precipitate (a) and single-layer MXene two-dimensional nanoplatelets (b) obtained after stripping in comparative example three and example three.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Comparative example 1
Adding 3g of lithium fluoride into 60ml of 9M hydrochloric acid, uniformly mixing to obtain a mixed solution, and slowly adding 3g of Ti into the mixed solution2AlC, stirring for 24 hours at 35 ℃, and then centrifugally washing to be neutral to obtain etched Ti2AlC phase material.
Weighing the above 0.5g etched Ti2And dispersing the AlC phase material in 15ml of distilled water, ultrasonically vibrating and stripping for 1h, and freeze-drying to obtain MXene precipitate.
Example one
0.5g of the etched Ti prepared in comparative example I was weighed2And dispersing the AlC phase material in a graduated container filled with 15ml of distilled water, heating in a fume hood until boiling, continuously supplementing water along with the evaporation of water in the heating process to maintain the graduation of the water in the container unchanged, namely maintaining the volume of the water unchanged in the evaporation process, stopping heating after boiling for 1h, cooling to room temperature, and freeze-drying to obtain the single-layer MXene nanosheet.
Referring to the attached figure 1, SEM images of MXene precipitate (a) and single-layer MXene two-dimensional nanosheets (b) obtained after stripping in the first comparative example and the first example show that MXene stripped by water vapor molecules has a loose two-dimensional nanosheet structure, and the thickness of a single layer is about 10 nm; in addition, the graph has almost no large particles stacked and is two-dimensional nanosheets, and the yield is close to 100%. Whereas the MXene precipitate in comparative example one mostly exhibited a massive blocky structure.
Referring to fig. 2, the X-ray diffraction patterns of the MXene precipitate (a) and the monolayer MXene two-dimensional nanosheet (b) obtained after the stripping of the comparative example one and the example one are shown in the figure, a distinct peak (5 °) can be observed in the stripped MXene two-dimensional material, which indicates that the interlayer spacing of MXene is increased.
Comparative example No. two
Adding 3g of lithium fluoride into 60ml of 9M hydrochloric acid, uniformly mixing to obtain a mixed solution, and slowly adding 3g of Ti into the mixed solution3SiC, stirring for 24 hours at 35 ℃, then centrifugally washing to be neutral,obtaining etched Ti3A SiC phase material.
Weighing the above 0.5g etched Ti3Dispersing the SiC phase material in 15ml of ethanol, carrying out ultrasonic oscillation and stripping for 1.5h, and carrying out freeze drying to obtain MXene precipitate.
Example two
0.5g of the etched Ti prepared in comparative example II was weighed3And dispersing the SiC phase material in a graduated container filled with 15ml of ethanol, heating the container in a fume hood until the SiC phase material is boiled, continuously supplementing ethanol along with the evaporation of the ethanol in the heating process to maintain the graduation of the ethanol in the container unchanged, namely maintaining the volume of the ethanol unchanged in the evaporation process, stopping heating after boiling for 1.5h, cooling the container to room temperature, adding 15ml of water after centrifugation because the ethanol is an organic solvent and cannot be freeze-dried, and greatly damaging an instrument, and freeze-drying the ethanol to obtain the single-layer MXene nanosheet.
Referring to fig. 3, SEM images of the MXene precipitate (a) and the monolayer MXene two-dimensional nanosheet (b) obtained after stripping in comparative example two and example two are shown, wherein the MXene molecularly stripped with ethanol vapor exhibits a loose two-dimensional nanosheet structure with a monolayer having a platelet thickness of about 5 nm; in addition, the graph has almost no large particles stacked and is two-dimensional nanosheets, and the yield is close to 100%. Whereas the MXene precipitate in comparative example two mostly exhibited a massive blocky structure.
Comparative example No. three
Adding 3g of lithium fluoride into 60ml of 9M hydrochloric acid, uniformly mixing to obtain a mixed solution, and slowly adding 3g of Ti into the mixed solution2AlC, stirring for 24 hours at 35 ℃, and then centrifugally washing to be neutral to obtain etched Ti2AlC phase material.
Weighing the above 0.5g etched Ti2And dispersing the AlC phase material in 15ml of acetone, ultrasonically oscillating and stripping for 2h, and freeze-drying to obtain MXene precipitate.
EXAMPLE III
0.5g of the etched Ti prepared in comparative example III was weighed2Dispersing AlC phase material in a graduated container filled with 15ml acetone, and adding into a fume hoodHeating until boiling, continuously adding acetone along with the evaporation of the acetone in the heating process to maintain the scale of the acetone in the container unchanged, namely maintaining the volume of the acetone in the evaporation process unchanged, stopping heating after boiling for 2 hours, cooling to room temperature, adding 15ml of water after centrifuging because the acetone is an organic solvent, and freeze-drying to obtain the single-layer MXene nanosheet.
Referring to fig. 4, SEM images of the MXene precipitate (a) and the single-layer MXene two-dimensional nanosheet (b) obtained after stripping in the third comparative example and the third example show that the MXene molecularly stripped with ethanol vapor has a loose two-dimensional nanosheet structure, and the single-layer thickness is about 10 nm; in addition, the graph has almost no large particles stacked and is two-dimensional nanosheets, and the yield is close to 100%. Whereas the MXene precipitate in comparative example three mostly exhibited a massive blocky structure.

Claims (4)

1. A method for preparing a single-layer Mxene nanosheet by using a steam stripping technology is characterized by comprising the following steps:
(1) dispersing the etched MAX phase material in a container with scales and a certain amount of solvent to obtain a mixed solution; the mass ratio of MAX phase materials to the solvent is 1: (20-30); the solvent is one or more of water, ethanol, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide and tetrabutylammonium hydroxide;
(2) and heating the mixed solution to boiling, continuously adding the solvent into the mixed solution along with the evaporation of the solvent in the heating process to maintain the scale of the solvent in the container unchanged, namely maintaining the volume of the solvent unchanged in the evaporation process, after boiling for 1-2 h, stopping heating, cooling to room temperature, and freeze-drying to obtain the single-layer Mxene nanosheet.
2. The method for preparing a single-layer Mxene nanosheet using vapor stripping technique as claimed in claim 1, wherein in the MAX phase material, the M layer comprises one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Sc; the A layer is Al or Si; the X layer is C or N element.
3. The method for preparing single-layer Mxene nanosheets using vapor stripping technique as claimed in claim 2, wherein the MAX phase material is Ti2AlC or Ti3SiC2。
4. The method for preparing the single-layer Mxene nanosheet by using the steam stripping technology as claimed in claim 1 or 2, wherein the thickness of the single-layer Mxene nanosheet prepared by the method is 1.5-100 nm.
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CN110090603A (en) * 2019-04-12 2019-08-06 湖北大学 A kind of MXene and graphene oxide composite aerogel and its preparation method and application
CN111591992A (en) * 2020-06-10 2020-08-28 哈尔滨工业大学 Single-layer MXene nanosheet and preparation method thereof

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CN110090603A (en) * 2019-04-12 2019-08-06 湖北大学 A kind of MXene and graphene oxide composite aerogel and its preparation method and application
CN111591992A (en) * 2020-06-10 2020-08-28 哈尔滨工业大学 Single-layer MXene nanosheet and preparation method thereof

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