CN110104650B - Ultrathin MXenes two-dimensional material with adjustable surface functional group and transition metal valence and preparation method thereof - Google Patents

Ultrathin MXenes two-dimensional material with adjustable surface functional group and transition metal valence and preparation method thereof Download PDF

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CN110104650B
CN110104650B CN201910353541.5A CN201910353541A CN110104650B CN 110104650 B CN110104650 B CN 110104650B CN 201910353541 A CN201910353541 A CN 201910353541A CN 110104650 B CN110104650 B CN 110104650B
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杨慧
李岚
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Tianjin University of Technology
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Abstract

The invention discloses an ultrathin MXenes two-dimensional layered material with adjustable surface functional groups and transition metal valence states and a preparation method thereof. The ultrathin two-dimensional layered material comprises MXenes, graphene, black phosphorus, silylene, ultrathin metals, ultrathin metal oxides, layered transition metal sulfides, layered transition metal selenides, layered transition metal tellurides, boron nitride and layered hydroxides. Compared with the prior art, the method adopts a physical stripping method to open the metal bond and strip the layered material, does not need corrosive acid, simultaneously realizes the synchronous regulation and control of the type of the surface functional group and the valence state of the metal, has the advantages of simple equipment, convenient operation, contribution to the mass preparation of two-dimensional ultrathin materials and the like, and has low preparation cost, environmental protection, safety and no toxicity.

Description

Ultrathin MXenes two-dimensional material with adjustable surface functional group and transition metal valence and preparation method thereof
Technical Field
The invention relates to ultrathin MXenes with adjustable surface functional groups and transition metal valence states and a preparation method thereof, in particular to a method for preparing an ultrathin MXenes two-dimensional layered material by opening a metal bond by a physical stripping method.
Background
Compared with bulk metal, the nano material has the characteristics of larger specific surface area, specific crystal face exposure, special size effect and the like, thereby showing higher activity, and therefore, the nano material has made great progress in the field of multiple applications. Among many nanomaterials, two-dimensional nanomaterials have been receiving attention in recent years because of their thickness decreasing from three-dimensional bulk to single or few layer nanoscale, creating unique electronic structures and exposing more active sites. Research into systems of two-dimensional materials such as ultra-thin metals, ultra-thin metal oxides, layered metal chalcogenides, hexagonal boron nitride, layered hydroxides, etc. is receiving increasing attention. The layered transition metal carbide (MXenes) is a novel graphite-like two-dimensional hotspot material, has rich chemical composition and high carrier mobility, and researchers at home and abroad carry out theoretical and experimental researches on MXenes phase materials, and finds that the layered transition metal carbide has a unique two-dimensional sheet layered structure, a larger specific surface area and good conductivity, and is expected to be widely applied to the fields of energy storage, catalysis, adsorption, hydrogen storage, sensors, novel polymer reinforcing base composite materials and the like.
M-X atomic layers in the MAX phase of the MXenes precursor are mainly covalent bonds and ionic bonds, the M-A atomic layers are mainly connected by metal bonds, and the M-A bonds are weaker than the covalent bonds between the M-X atomic layers and stronger than the Van der Waals force between graphite layers. Therefore, the common physical mechanical stripping method cannot open the metal key to realize an ultra-thin structure. Compared with the M-X bond, the bonding force of the M-A bond is weaker, so that the reaction activity of the atoms in the layer A is relatively higher, and the peeling can be realized through etching, thereby obtaining the MXenes with a layered structure. People usually adopt an acid chemical liquid phase etching method to strip A layer atoms to prepare MXenes ultrathin layers, but the method has three characteristics: firstly, MXenes obtained by HF corrosion are easy to adsorb hydrophilic functional groups such as-F, -O, -OH and the like, and multiple related researches report that the variety of MXenes surface functional groups prepared by a chemical etching method obviously influences the multiple properties such as electro-catalytic performance, lithium ion battery capacity, electrochemical capacity, energy band structure, electron transmission characteristic, light absorption performance and the like. Secondly, low-coordination transition metal ions exposed on the surface in the corrosion process are easily oxidized, so that a large number of active sites disappear; moreover, the higher the corrosion temperature is, the more serious the oxidation is, so that the conductivity of the material is reduced, and the semimetal characteristic predicted by theory no longer becomes an advantage, so that the activity is reduced; in addition, the MXenes structural stability is also affected by the transition metal oxidation. The surface adsorption functional group and the transition metal oxidation are the key for restricting the potential application of the two-dimensional layered MXenes in the multiple fields, which is also a problem that the MXenes are crucial in material preparation and performance research all the time. Thirdly, the HF solution used in the experiment has high toxicity and strong corrosivity, and has certain danger in actual operation. Therefore, the conventional acid etching method for interlayer peeling has the above drawbacks. In view of the above, a green and safe preparation method capable of preventing oxidation of surface low-valence metal in the precursor delamination process and effectively regulating and controlling surface functional groups is sought, and MXenes faces a problem to be solved urgently.
Disclosure of Invention
In order to overcome the above disadvantages and shortcomings of the prior art, an object of the present invention is to provide an ultra-thin MXenes two-dimensional material with adjustable surface functional groups and transition metal valence, which has the advantages of surface functional group regulation and transition metal valence regulation. The second purpose of the invention is to provide the preparation method of the ultrathin MXenes two-dimensional layered material, which has the advantages of simple equipment, convenient operation, easy realization of the regulation and control of the valence states of the functional group and the transition metal, contribution to the mass preparation of the two-dimensional ultrathin material, low preparation cost, greenness and no toxicity.
The purpose of the invention is realized by the following technical scheme:
an ultrathin MXenes two-dimensional material with adjustable surface functional groups and transition metal valence states comprises an ultrathin MXenes two-dimensional material with adjustable surface functional groups, an ultrathin MXenes two-dimensional material with adjustable transition metal valence states and an ultrathin MXenes two-dimensional material with adjustable surface functional groups and transition metal valence states; the ultrathin MXenes two-dimensional material is prepared directly in one step by adopting a low-temperature ultrahigh-pressure physical stripping method.
Further, the ultrathin two-dimensional material prepared by the preparation method also comprises graphene, black phosphorus, silylene, ultrathin metals, layered transition metal oxides, layered transition metal sulfides, layered transition metal selenides, layered transition metal tellurides, boron nitride and layered hydroxides.
A preparation method of ultrathin MXenes two-dimensional material with adjustable surface functional group and transition metal valence comprises the following steps:
(1) using layered precursors (e.g. MAX: Ti)3AlC2Etc.) as raw materials, ultrasonically dispersing the layered precursor in a solvent with a certain concentration, and realizing the regulation and control of the surface adsorption functional group type and the metal valence state by changing the functional group type and the redox property of the solvent;
(2) and (2) pouring the precursor dispersed in the solvent in the step (1) into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, directly preparing the ultrathin two-dimensional MXenes material in one step by adopting a low-temperature ultrahigh-pressure physical stripping method, physically stripping the layered precursor by controlling the temperature of a circulating water bath, ultrahigh-pressure conditions, stripping times and concentration to obtain a homogeneous solution with a certain concentration, adding a proper amount of deionized water, centrifuging, washing for several times, and carrying out vacuum freeze drying, and finally directly preparing the two-dimensional ultrathin MXenes material with the surface adsorption functional group and the metal valence state simultaneously adjustable in one step.
Further, according to the preparation method of the ultrathin MXenes two-dimensional material with the adjustable surface functional group and transition metal valence, in the step (1), the particle diameter of the layered precursor is below 100um so as not to block the outlet of the valve; the types of the functional groups of the solvent are various functional groups, and the regulation and control of the surface adsorption functional groups are realized; the properties of the solvent comprise oxidizability, neutrality and reducibility, thereby realizing the regulation and control of the high and low valence states of the transition metal in the physical stripping process.
Further, in the preparation method of the ultrathin MXenes two-dimensional material with the surface functional group and the transition metal valence adjustable, the continuous flow crusher in the step (2) has the following process parameters, and the low-temperature circulating water bath is adopted: 1-4 ℃, and ultrahigh pressure conditions: 50-200 MPa; the number of peeling times: 2-10 times; concentration: 0.001-1 mg/ml.
Further, the preparation method of the ultrathin MXenes two-dimensional material with the adjustable surface functional group and transition metal valence state is used for preparing the ultrathin two-dimensional material with the specific surface functional group and transition metal valence state, and the ultrathin two-dimensional material comprises MXenes, graphene, black phosphorus, silylene, ultrathin metal, layered transition metal oxide, layered transition metal sulfide, layered transition metal selenide, layered transition metal telluride, boron nitride and layered hydroxide.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention uses a low-temperature ultrahigh-pressure method to physically peel off the layered precursor to prepare the ultrathin MXenes. The traditional chemical etching method has the following characteristics that the HF solution used in the experiment has high toxicity, and the obtained MXene has two characteristics: the surface contains functional groups such as hydroxyl, fluorinion and the like; meanwhile, the low-valence transition metal is easy to oxidize. The method greatly restricts the exhibition of excellent performance of the two-dimensional ultrathin MXenes and the expansion of the application field. The method has simple and convenient process, and can react in a low-temperature circulating water bath, and the sample is nanocrystallized under the three effects of shearing, cavitation and collision by utilizing ultrahigh pressure energy and still keeps the activity of the original substance. The M-A metal bond is easily opened by strong shock waves generated by the cavitation under the ultrahigh pressure, the energy required for stripping the precursor MAX is achieved, and the layered material is stripped. This eliminates the need for corrosive acids, while achieving thinning and improved yield. The method provides a new idea for the preparation and synthesis of hot spot materials MXenes and other two-dimensional layered materials.
(2) The method uses a low-temperature ultrahigh-pressure method to physically peel off the layered precursor to prepare the ultrathin MXenes, and can realize synchronous regulation and control of MXenes surface functional groups and transition metal valence states without using corrosive acid and further surface chemical modification steps. By changing the type and redox property of the treatment solvent, the type of the surface adsorption functional group can be designed, the valence state of the metal ions can be regulated and controlled to keep the activity of the metal ions, and the surface structure and performance of the MXenes material can be regulated and controlled finally, so that the method has great significance for realizing the two-dimensional material with specific function.
(3) The ultrathin MXenes are international hotspot materials, the application of the ultrathin MXenes relates to multiple disciplines such as materials science, chemistry, physics, biology, sensing, energy and the like, and related scientific problem researches are related to each other, so that the ultrathin MXenes prepared by the method and the researches thereof can promote the development of the multiple disciplines, particularly the development of the ultrathin MXenes with specific surface structures, and provide feasibility for designing two-dimensional layered materials with specific application guide.
Drawings
Fig. 1 is a schematic flow chart of the invention for preparing ultrathin MXenes.
FIG. 2 is an XPS plot of ultra-thin MXenes prepared according to the present invention.
Fig. 3 is an SEM image of ultra-thin MXenes prepared by the present invention.
Figure 4 is an AFM image of ultra-thin MXenes prepared in accordance with the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the two-dimensional layered material of the present invention are not limited thereto.
Example 1
The ultra-thin MXenes of the embodiment has Ti3C2The preparation method of the material low-temperature ultrahigh-pressure physical stripping comprises the following steps:
(1) using a layered precursor Ti3AlC2The particle diameter is less than 100 um. Mixing Ti3AlC2Ultrasonically dispersing in solvent with certain concentration, wherein the solvent is tetramethyl ammonium hydroxide with reducibility and concentration of 0.001 mg/ml.
(2) The method for directly preparing the ultrathin two-dimensional MXenes material by one step by using a low-temperature ultrahigh-pressure physical stripping method comprises the following steps: dispersing Ti in tetramethylammonium hydroxide in the step (1)3AlC2Pouring the solution into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, wherein the continuous flow crusher has the following technological parameters, and performing low-temperature circulating water bath: 4 ℃, ultrahigh pressure conditions: 200 MPa; the number of peeling times: 2 times; concentration: 0.001 mg/ml.
(3) After stripping, adding a proper amount of deionized water, centrifuging, washing for 2 times, and then carrying out vacuum freeze drying, and finally directly preparing the two-dimensional ultrathin Ti with methyl, nitrogen-containing functional groups and low-valence titanium adsorbed on the surface in one step3C2A material.
Fig. 1 is a flow chart of the method for preparing ultrathin MXenes by the low-temperature ultrahigh-pressure physical stripping method, and the method comprises a layered precursor 11, different solvents 21 and an ultrathin MXenes material 31 prepared by the stripping method. The layered precursor is peeled into the ultrathin MXenes material under the action of cavitation shear force.
FIG. 2 shows the ultra-thin Ti prepared by the method of the present invention and the conventional HF etching method3C2Comparative XPS test of (1). XPS spectra of characteristic elements Ti, C, N and O are obtained by testing, and ultra-thin Ti obtained by HF chemical corrosion method is discovered3C2The surface is rich in-O and-OH functional groups, and a large amount of low coordination metal Ti is oxidized into TiO2. And stripping Ti in reducing solvent (TMAH) by adopting low temperature and ultrahigh pressure3AlC2The obtained ultra-thin Ti3C2The surface detection does not contain F element, but is rich in N group, and simultaneously adsorbs a small amount of oxygen-containing group, which shows that the method can effectively regulate and control MXene surface adsorption functional groups; most importantly, the low coordination metal Ti still keeps the original valence states of +2 and +3,even metal Ti atoms appear, further illustrating that the low-temperature ultrahigh-pressure stripping method can synchronously regulate and control the valence state of the transition metal. Therefore, the low-temperature ultrahigh-pressure method can simultaneously change the surface functional group and regulate the valence state of the Ti metal by one step.
FIG. 3 shows the ultra-thin Ti prepared by the present invention3C2SEM image of (d). As can be seen from the figure, the layered precursor Ti3AlC2The size of the raw material is about 8 μm, Ti3C2The size of the nanosheets is about 1-2 μm.
FIG. 4 shows the ultra-thin Ti prepared by the present invention3C2AFM test chart (5). As can be seen from the figure, Ti was exfoliated at a pressure of 200MPa3AlC2Three times the solution to obtain Ti with the thickness of about 3.5nm and the size of 1-2 μm3C2Nanosheets. Thinner Ti can be obtained by increasing the processing pressure and the processing times3C2。
Example 2
This example is a two-dimensional ultrathin SnSe whose surface functional group and transition metal valence can be synchronously controlled2(MoS2And WSe2Etc.) a method for producing a physical peeling comprising the steps of:
(1) using lamellar blocks of SnSe2The particle diameter is less than 100 um. The bulk SnSe2Ultrasonically dispersing in a solvent with a certain concentration, wherein the solvent is water, and is neutral with the concentration of 1 mg/ml.
(2) Direct preparation of ultrathin two-dimensional SnSe by low-temperature ultrahigh-pressure physical stripping method2Materials: SnSe dispersed in water in the step (1)2Pouring the solution into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, wherein the continuous flow crusher has the following technological parameters, and performing low-temperature circulating water bath: 1 ℃, ultrahigh pressure conditions: 50 MPa; the number of peeling times: 10 times; concentration: 1 mg/ml.
(3) After stripping, adding a proper amount of deionized water, centrifuging, washing for 3 times, and then carrying out vacuum freeze drying, and finally directly preparing two-dimensional ultrathin SnSe with the surface adsorbed with hydroxyl functional groups and tin with a valence of +4 and the thickness of about 2nm by one step2A material.
Example 3
The preparation method of the two-dimensional ultrathin metal Zn physical stripping with synchronously controllable surface functional group and transition metal valence state of the embodiment comprises the following steps:
(1) layered block Zn is used as a raw material, and the particle diameter is below 100 um. Ultrasonically dispersing the layered graphite in a solvent with a certain concentration, wherein the solvent is sodium sulfite solution with reducibility and the concentration of 0.1 mg/ml.
(2) Directly preparing an ultrathin two-dimensional Zn nanosheet by a low-temperature ultrahigh-pressure physical stripping method: pouring the layered block Zn solution dispersed in the neutral water in the step (1) into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, wherein the continuous flow crusher has the following process parameters, and performing low-temperature circulating water bath: 3 ℃, ultrahigh pressure condition: 100 MPa; the number of peeling times: 6 times; concentration: 0.1 mg/ml.
(3) And after the stripping is finished, adding a proper amount of deionized water, centrifuging, washing for 3 times, and then carrying out vacuum freeze drying, thus finally directly preparing the two-dimensional ultrathin Zn nanosheet with the surface adsorbing a small amount of hydroxyl and sulfydryl and the thickness of about 2nm in one step.
Example 4
The preparation method for physically stripping the two-dimensional ultrathin layered transition metal oxide molybdenum oxide (Ni, Co, Mn, Mo, Fe, etc.) with synchronously controllable surface functional groups and transition metal valence states in the embodiment comprises the following steps:
(1) by using layered block MoO3The particle diameter is less than 100 um. The block body MoS2Ultrasonically dispersing in a solvent with a certain concentration, wherein the solvent is ethanol and is neutral, and the concentration is 0.01 mg/ml.
(2) Low-temperature ultrahigh-pressure physical stripping method for directly preparing ultrathin two-dimensional MoO3Materials: dispersing MoO in neutral ethanol in the step (1)3Pouring the solution into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, wherein the continuous flow crusher has the following technological parameters, and performing low-temperature circulating water bath: 2 ℃, ultrahigh pressure conditions: 150 MPa; the number of peeling times: 4 times; concentration: 0.5 mg/ml.
(3) And after the stripping is finished, adding a proper amount of deionized water, centrifuging, washing for 3 times, and then carrying out vacuum freeze drying, thus finally directly preparing the two-dimensional ultrathin layered double molybdenum hydroxide LDH with the surface being rich in hydroxyl functional groups and +6 valence molybdenum and the thickness being about 2.5nm in one step.
Example 5
The preparation method of the two-dimensional ultrathin graphene physical exfoliation with the synchronously controllable surface functional group and transition metal valence state of the embodiment comprises the following steps:
(1) graphite is used as a raw material, and the diameter of the graphite is below 100 um. Ultrasonically dispersing graphite in a solvent with a certain concentration, wherein the solvent is ammonia water, and the concentration of the ammonia water is 0.1 mg/ml.
(2) Directly preparing the ultrathin two-dimensional graphene material by a low-temperature ultrahigh-pressure physical stripping method: pouring the layered graphite solution dispersed in the neutral ethanol in the step (1) into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, wherein the continuous flow crusher has the following process parameters, and performing low-temperature circulating water bath: 2 ℃, ultrahigh pressure conditions: 150 MPa; the number of peeling times: 8 times; concentration: 0.5 mg/ml.
(3) And after stripping, adding a proper amount of deionized water, centrifuging, washing for 3 times, and then carrying out vacuum freeze drying, and finally directly preparing the two-dimensional ultrathin graphene which is rich in amino groups and a small amount of hydroxyl functional groups on the surface and has the thickness of about 1.5nm in one step.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (3)

1. The preparation method of the ultrathin MXenes two-dimensional material is characterized by comprising the ultrathin MXenes two-dimensional material with adjustable surface functional groups, the ultrathin MXenes two-dimensional material with adjustable transition metal valence and the ultrathin MXenes two-dimensional material with adjustable surface functional groups and transition metal valence;
the preparation method of the ultrathin MXenes two-dimensional material is a low-temperature ultrahigh-pressure physical stripping one-step method and comprises the following steps:
1) the layered precursor is adopted as a raw material, the layered precursor is dispersed in a solvent with a certain concentration in an ultrasonic mode, and the regulation and control of the surface adsorption functional group type and the metal valence state are realized by changing the functional group type and the redox property of the solvent;
2) pouring the precursor dispersed in the solvent in the step 1) into a container of a low-temperature ultrahigh-pressure continuous flow crusher at a low speed, directly preparing the ultrathin two-dimensional MXenes material in one step by adopting a low-temperature ultrahigh-pressure physical stripping method, physically stripping the layered precursor by controlling the temperature of a circulating water bath, ultrahigh-pressure conditions, stripping times and concentration to obtain a homogeneous solution with a certain concentration, adding a proper amount of deionized water, centrifuging, washing for several times, and carrying out vacuum freeze drying to finally directly prepare the two-dimensional ultrathin MXenes material with the surface adsorption functional group and the metal valence state simultaneously adjustable;
the process parameters of the continuous flow crusher in the step 2) are as follows, and the water bath is circulated at low temperature: 1-4 ℃, and ultrahigh pressure conditions: 50-200 MPa; the number of peeling times: 2-10 times; concentration: 0.001-1 mg/ml.
2. The method for preparing the ultrathin MXenes two-dimensional material as claimed in claim 1, wherein the method comprises the following steps: the functional group types of the solvent in the step 1) are various functional groups, the regulation and control of the surface adsorption functional group can be realized, and the properties of the functional group of the solvent comprise oxidizability, neutrality and reducibility, so that the regulation and control of the high and low valence states of the transition metal in the physical stripping process can be realized.
3. The method for preparing the ultrathin MXenes two-dimensional material as claimed in claim 1, wherein the method comprises the following steps: the particle diameter of the layered precursor in the step 1) is below 100 um.
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