CN108423645B - Three-dimensional MXene and general synthesis method thereof - Google Patents
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Abstract
A three-dimensional MXene and a general synthetic method thereof belong to the field of nano materials. The three-dimensional MXene is a porous hierarchical three-dimensional structure formed by three-dimensionally and tightly crosslinking two-dimensional MXene. The preparation method comprises the following steps: atomizing MXene suspension into aerosol micro-droplets with the size of about several microns by using an ultrasonic atomizer, and rapidly drying at the high temperature of 800 ℃ in an inert atmosphere to obtain the three-dimensional MXene with the controllable structure and size. The three-dimensional MXene obtained by the method overcomes the basic problem that two-dimensional MXene is easy to stack and agglomerate under van der Waals force, and lays a foundation for preparation, processing and application in various aspects of high-performance functional materials based on MXene.
Description
Technical Field
The invention belongs to the field of nano materials, and relates to three-dimensional MXene and a general synthesis method thereof.
Background
Nanomaterials have received much attention because of their size effects, their physicochemical properties far superior to those of macroscopic bulk materials. The performance of the functional nano material depends on the appearance, size and crystalline phase structure of the functional nano material to a great extent, the microstructure of the functional nano material is finely regulated, and the realization of structural design and controllable construction become the hot field of scientific research of nano materials in recent years.
MXene is a novel two-dimensional crystal of transition metal carbide or nitride, and has a two-dimensional structure similar to that of graphene. Having the chemical formula Mn+1Xn(n is 1,2,3, M is a transition metal element, and X is carbon or nitrogen). The material is obtained by acid etching of a MAX phase of a layered ceramic material, has excellent electrical, mechanical and magnetic properties and the like, and can be used for energy storage and electromagnetic shielding in recent yearsThe method is widely applied to the fields of water treatment, gas/biological sensing, photoelectrochemical catalysis and the like.
The MXene two-dimensional nanostructure endows the MXene with unique performance, but MXene lamella is extremely easy to irreversibly stack and agglomerate under the action of van der Waals force, so that the specific surface area, the dispersibility and the ion conduction characteristic of the MXene lamella are greatly reduced, the efficient utilization of an interface is limited, and the macroscopic performance and the processing performance of the MXene lamella in various fields are seriously influenced and limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a general synthesis method of three-dimensional MXene with anti-stacking and agglomeration performances, the prepared product is formed by three-dimensionally communicating and assembling two-dimensional MXene, and the product has a flower-shaped or spherical hierarchical porous structure, so that the problems of layer-by-layer stacking and agglomeration of MXene are fundamentally solved, and the fundamental problem which puzzles MXene performance and various application aspects is solved. The synthesis method is green and environment-friendly, low in energy consumption, easy to control and universal, and can be used for large-scale production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the three-dimensional MXene has a flower-like or spherical hierarchical porous structure with the size of 0.2-50 μ M, and the general structural formula of the three-dimensional MXene is Mn+1XnOr (M)1,M2)n+1XnOr Mn+1(X1,X2)nOne or a combination of two or more of them.
Said Mn+1XnWherein M ═ Ti, Nb, V, Mo, Zr, Cr, W, Ta; n is 1,2, 3; x ═ C, N.
Said (M)1,M2)n+1XnIn, M1,M2＝Ti,Nb,V,Mo,Zr,Cr,W,Ta；n＝1,2,3；X＝C,N。
Said Mn+1(X1,X2)nWherein M ═ Ti, Nb, V, Mo, Zr, Cr, W, Ta; n is 1,2, 3; x1,X2＝C,N。
A preparation method of three-dimensional MXene comprises the following steps:
1) the concentration is 0.5-20mg mL by an ultrasonic atomizer-1The MXene suspension is atomized into aerosol micro-droplets with the size of about several microns, wherein the solvent of the MXene suspension is at least one of water or alcohol containing 1-11 carbon atoms.
The auxiliary agent can also be added into MXene suspension, and then atomized into aerosol micro-droplets by an ultrasonic atomizer, wherein the auxiliary agent is used for adjusting the structure and the properties of the aerosol micro-droplets. The auxiliary agent comprises a surfactant, a high molecular polymer, micro/nano particles and the like, and the mass ratio of the auxiliary agent to the MXene suspension is 0.1-10: 1.
2) Blowing the aerosol micro-droplets obtained in the step 1) into a high-temperature furnace with a preset temperature by taking inert gas as carrier gas, and quickly drying to obtain three-dimensional MXene particles, wherein the preset temperature of the high-temperature furnace is 400-800 ℃. The inert gas is at least one of nitrogen, argon or helium, and the flow rate of the carrier gas is 0.1-1.0L h-1。
Compared with the prior art, the invention solves the problems of preparation, processing and application of the two-dimensional MXene, and has the beneficial effects that:
(1) in the structure, MXenes are interwoven and mutually supported in a three-dimensional network mode, so that the lamination and agglomeration caused by Van der Waals interaction between the MXenes can be effectively inhibited; meanwhile, due to the steric hindrance effect caused by the rough surface, agglomeration among the three-dimensional MXene particles can be well inhibited.
(2) The prepared three-dimensional MXene has a specific surface area superior to that of two-dimensional MXene, shows good dispersibility in solvents with different densities and different polarities, is not easy to agglomerate under a solid condition, and has excellent processing characteristics.
(3) The method can realize fine regulation and control of the structure, the size and the like of the three-dimensional MXene, has simple process, can realize continuous production, is green and environment-friendly in process and is easy for large-scale production; has wide application prospect in the fields of energy storage, catalysis, photoelectric materials, biological medicines, electromagnetic shielding, wave-absorbing materials and the like.
Drawings
FIG. 1 is a scanning electron microscope photograph of flower-like three-dimensional MXene prepared at 400 ℃ in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of flower-like three-dimensional MXene prepared at 600 ℃ in example 2 of the present invention;
FIG. 3 is a scanning electron microscope photograph of flower-like three-dimensional MXene prepared at 800 ℃ in example 3 of the present invention;
FIG. 4 is an electron micrograph of spherical three-dimensional MXene prepared at 600 ℃ in example 4 of the present invention; FIG. (a) is a scanning electron micrograph of spherical three-dimensional MXene; fig. (b) is a high-power scanning electron micrograph of spherical three-dimensional MXene.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention, and further explains the technical solution, the implementation process and the principle, etc. as follows. It is to be understood, however, that within the scope of the present invention, each of the above-described features of the present invention and each of the features described in detail below (examples) may be combined with each other to form new or preferred embodiments.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of flower-like three-dimensional MXene
1) MXene was dispersed in water to a concentration of 10mg mL-1A suspension of (a).
2) The MXene suspension in 1) was atomized into aerosol micro-droplets of size of about several microns using an ultrasonic atomizer (3.2W, Sinnsonic DP 30).
3) And (3) blowing the aerosol micro-droplets obtained in the step (2) into a tubular furnace with a preset temperature of 400 ℃ by using Ar gas as a carrier gas to rapidly dry the aerosol micro-droplets. The obtained product is three-dimensional structure particles with flower-like appearance, the average size of which is about 3.5 mu m, and the three-dimensional structure particles are assembled by three-dimensional close crosslinking of MXene.
Example 2 preparation of flower-like three-dimensional MXene
1) MXene was dispersed in water to a concentration of 5mg mL-1A suspension of (a).
2) The MXene suspension in 1) was atomized into aerosol micro-droplets of size of about several microns using an ultrasonic atomizer (3.2W, Sinnsonic DP 30).
3) And (3) blowing the aerosol micro-droplets obtained in the step (2) into a tubular furnace with a preset temperature of 600 ℃ by using Ar gas as a carrier gas to rapidly dry the aerosol micro-droplets. The obtained product is three-dimensional structure particles with flower-like appearance, the average size of which is about 3.5 mu m, and the three-dimensional structure particles are assembled by three-dimensional close crosslinking of MXene.
Example 3 preparation of flower-like three-dimensional MXene
1) MXene was dispersed in water to a concentration of 20mg mL-1A suspension of (a).
2) The MXene suspension in 1) was atomized into aerosol micro-droplets of size of about several microns using an ultrasonic atomizer (3.2W, Sinnsonic DP 30).
3) And (3) blowing the aerosol micro-droplets obtained in the step (2) into a tubular furnace with a preset temperature of 800 ℃ by using Ar gas as a carrier gas to rapidly dry the aerosol micro-droplets. The obtained product is three-dimensional structure particles with flower-like appearance, the average size of which is about 3.5 mu m, and the three-dimensional structure particles are assembled by three-dimensional close crosslinking of MXene.
Example 4 preparation of spherical three-dimensional MXene
1) MXene and accessory ingredient polyvinylpyrrolidone are dispersed in water to prepare MXene with the concentration of 5mg mL-1The concentration of polyvinylpyrrolidone is 2mg mL-1A suspension of (a).
2) The mixed suspension of MXene and the adjuvant polyvinylpyrrolidone described in 1) was atomized with an ultrasonic atomizer (3.2W, Sinnsonic DP30) into aerosol microdroplets of the order of a few micrometers in size.
3) Blowing the aerosol micro-droplets obtained in the step 2) into a tubular furnace with the preset temperature of 600 ℃ by taking nitrogen as a carrier gas so as to rapidly dry the aerosol micro-droplets. The obtained product is three-dimensional structure particles with spherical appearance, the average size of which is about 3-4 mu m, and the three-dimensional structure particles are assembled by three-dimensional close crosslinking of MXene.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (2)
1. The three-dimensional MXene is characterized in that the three-dimensional MXene has a flower-like or spherical hierarchical porous structure, the size of the three-dimensional MXene is 0.2-50 mu M, and the general structural formula of the three-dimensional MXene is Mn+1XnOr (M)1,M2)n+1XnOr Mn+1(X1,X2)nOne or a combination of two or more of them;
said Mn+1XnWherein M ═ Ti, Nb, V, Mo, Zr, Cr, W, Ta; n is 1,2, 3; x ═ C, N;
said (M)1,M2)n+1XnIn, M1,M2＝Ti,Nb,V,Mo,Zr,Cr,W,Ta；n＝1,2,3；X＝C,N；
Said Mn+1(X1,X2)nWherein M ═ Ti, Nb, V, Mo, Zr, Cr, W, Ta; n is 1,2, 3; x1,X2＝C,N；
The preparation method of the three-dimensional MXene comprises the following steps:
1) atomizing MXene suspension into aerosol micro-droplets by using an ultrasonic atomizer, wherein the solvent of the MXene suspension is at least one of water or alcohol containing 1-11 carbon atoms;
2) blowing the aerosol micro-droplets obtained in the step 1) into a high-temperature furnace with a preset temperature by taking inert gas as carrier gas, and quickly drying to obtain three-dimensional MXene particles, wherein the preset temperature of the high-temperature furnace is 400-800 ℃.
2. The three-dimensional MXene of claim 1, wherein in step 1), an auxiliary agent can be added into the MXene suspension, and then the MXene suspension is atomized into aerosol micro-droplets by an ultrasonic atomizer, wherein the auxiliary agent is used for adjusting the structure and the properties of the aerosol micro-droplets; the mass ratio of the auxiliary agent to the MXene suspension is 0.1-10: 1.
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| CN109152318B (en) * | 2018-10-16 | 2019-12-20 | 青岛大学 | Preparation method of novel electromagnetic wave absorption material |
| CN109592684B (en) * | 2018-12-18 | 2020-09-01 | 燕山大学 | Petal spherical titanium carbide Ti3C2Mxene and preparation method and application thereof |
| CN110342516A (en) * | 2019-07-09 | 2019-10-18 | 哈尔滨工程大学 | A kind of MXene material of three-dimensional crosslinking structure and preparation method thereof |
| CN110606487A (en) * | 2019-10-16 | 2019-12-24 | 大连理工大学 | Honeycomb three-dimensional porous MXene with controllable pore diameter and general synthesis method thereof |
| CN113387357A (en) * | 2021-07-22 | 2021-09-14 | 江西理工大学 | Preparation method of MXene folded nanospheres |
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| CN107522202A (en) * | 2017-08-07 | 2017-12-29 | 四川大学 | A kind of stratiform two-dimensional material MXene preparation method and applications |
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