CN115385337A - Method for modifying MXene and application thereof - Google Patents
Method for modifying MXene and application thereof Download PDFInfo
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- CN115385337A CN115385337A CN202210992352.4A CN202210992352A CN115385337A CN 115385337 A CN115385337 A CN 115385337A CN 202210992352 A CN202210992352 A CN 202210992352A CN 115385337 A CN115385337 A CN 115385337A
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Abstract
The invention discloses a method for modifying MXene and application thereof. Wherein, the MXene modification is carried out by using amino acid, and the method comprises the following steps: mixing MXene nanosheets and amino acid molecules in a solution to complete modification. Starting from the root cause of MXene oxidation reaction, the invention realizes the adsorption of amino acid molecules on the MXene surface by utilizing the hydrogen bond and coordination bond action between the amino acid molecules and the MXene, occupies the attack reaction sites of water and oxygen in the oxidation process, further prevents the MXene from being oxidized and degraded in water, improves the oxidation resistance of the MXene, and further improves the stability of structure and performance. The modification method provided by the invention does not change the inherent properties of MXene such as morphology and the like, not only can greatly improve the oxidation resistance of the MXene material, but also the prepared film keeps the original good mechanical property, and the electromagnetic shielding performance is basically not changed or slightly reduced.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a method for modifying MXene and application thereof.
Background
Two-dimensional (2D) transition metal carbide/nitride (MXenes) is of increasing interest for its excellent performance, typically obtained by selective extraction of a layer from a three-dimensional MAX phase by a mixture of hydrofluoric or hydrochloric acid and lithium fluoride. The groups are classified into two groups according to whether there is a terminal group at the surface terminal, one is M n+1 X n The other class is M n+1 X n T x Wherein M represents transition metal (such as Ti, V, cr, nb, mo, etc.), and X represents C, N, T x Is a terminal group (e.g., -OH, -O or-F), n is usually an integer between 1 and 3, and x cannot be accurately quantified. As one of the two-dimensional materials, MXene has a two-dimensional layered structure similar to graphene, high electrical conductivity and large surface area, but unlike graphene, MXene nanomaterials have abundant hydrophilic surface functional groups, which make it easy to process and prepare into composite materials. Therefore, the method has good application prospect in the fields of energy storage, sensors, electromagnetic interference shielding, water purification, photocatalysis and the like. Ti 3 C 2 T x Has excellent intrinsic conductivity (4500 Scm) -1 ) The compound is one of the MXenes families which is researched more, and has great application prospect in the field of electromagnetic shielding.
However, MXene is limited in its practical application by its extreme susceptibility to oxidation and poor mechanical properties. The existing mechanism shows that water and oxygen accelerate the oxidation to generate titanium oxide, and the oxidation process destroys MXene structure, thereby deteriorating the original excellent properties. Therefore, how to solve the problem that MXene is easily oxidized and how to improve the mechanical properties of MXene so as to maintain the performance stability of MXene in use is a bottleneck problem of MXene development. In order to solve the problem that MXene is easily oxidized, researchers cover different substances on the surface of MXene to reduce the contact chance of MXene with oxygen and water and prevent MXene from being oxidized. However, the method only solves the problem of MXene oxidation, and does not solve the problem of poor mechanical properties of MXene at the same time. Therefore, the search for new solutions to improve the stability and mechanical properties of MXene is an urgent task for the development of MXene.
Disclosure of Invention
In view of the above technical problems, the present invention provides a method for modifying MXene and applications thereof, so as to simultaneously improve oxidation resistance and mechanical properties of MXene materials.
In order to achieve the purpose, the invention adopts the technical scheme that:
in one aspect, the invention provides a method for modifying MXene, wherein the MXene is modified by amino acid, and the method for modifying MXene comprises the following steps:
mixing MXene nanosheets and amino acid molecules in a solution to react, and finishing modification.
As a preferable embodiment, the time for completing the modification of the MXene nanosheets and the amino acid molecules in the mixed reaction in the solution is more than or equal to 24 hours.
As a preferred embodiment, the amino acid molecule is in excess relative to the MXene nanoplatelets;
in certain specific embodiments, the excess is 0.01 to 0.03mol of amino acid per 0.1g of MXene nanosheets in solution;
preferably, the concentration of the amino acid molecules in the solution is 0.01 mol/L-0.3 mol/L.
As a preferred embodiment, the MXene nanoplatelets are selected from at least one of multilayered MXene nanoplatelets and monolayer MXene nanoplatelets.
As preferably practicedIn an embodiment, the MXene is Ti 3 C 2 T x 。
As a preferred embodiment, the Ti 3 C 2 T x Prepared by a liquid phase stripping method or a molten salt method;
preferably, the liquid phase lift-off process is by etching MAX phase Ti 3 AlC 2 The powder specifically comprises the following steps:
adding a MAX phase Ti 3 AlC 2 Adding the powder into an etchant solution, stirring for 24-48 h, and centrifuging and washing until the pH value is more than or equal to 6;
preferably, the etchant solution is a solution obtained by dissolving LiF in hydrochloric acid.
As a preferred embodiment, the amino acid molecule is selected from at least one of alanine, glycine, lysine, glutamic acid, arginine, histidine and cysteine.
In the technical solution of the present invention, the solution is conventionally selected in the art. The solvent of the solution is organic solvent or water; wherein the organic solvent comprises any one or more of a polar solvent and a nonpolar solvent, and the polar solvent comprises any one or more of a polar protic solvent and a polar aprotic solvent; the solution is preferably an aqueous solution.
In certain specific embodiments, the specific steps of the method for modifying MXene comprise:
and dispersing the stripped multilayer MXene nanosheets and/or single-layer MXene nanosheets in a solvent, then adding an amino acid solution, mixing uniformly and standing to obtain the MXene modified by the amino acid molecules.
In yet another aspect, the present invention provides MXene modified with amino acid molecules obtained by the above method.
In another aspect, the invention provides an amino acid molecule modified MXene film prepared from the amino acid molecule modified MXene.
In some specific embodiments, the MXene film modified by the amino acid molecules is prepared by mixing MXene nanosheets and amino acid molecules in a solution for reaction and then performing vacuum filtration.
In another aspect, the invention provides an application of the MXene film modified by the amino acid molecules in preparing electromagnetic shielding materials.
The technical scheme has the following advantages or beneficial effects:
starting from the root cause of MXene oxidation reaction, MXene and amino acid molecules are mixed in aqueous solution to realize modification to obtain MXene modified by the amino acid molecules, the adsorption of the amino acid molecules on the MXene surface is realized by utilizing the hydrogen bond and coordination bond action between the amino acid molecules and the MXene, and the amino acid molecules occupy the attack reaction sites of water and oxygen in the oxidation process, so that the oxidation and degradation of the MXene in water are prevented, the oxidation resistance of the MXene is improved, and the stability of the structure and performance of the MXene in the aqueous solution and the air is further improved.
The modification method provided by the invention does not change the inherent properties of MXene such as morphology and the like, not only can greatly improve the oxidation resistance of the MXene material, but also the prepared film keeps the original good mechanical property, and the electromagnetic shielding property is basically not changed or slightly reduced.
Drawings
FIG. 1A is a scanning electron micrograph of MXene modified with a newly prepared cysteine molecule in example 1 of the present invention;
FIG. 1B is a scanning electron microscope image of the aqueous solution of MXene modified by cysteine molecule prepared in example 1 of the present invention after being left at room temperature for 2 weeks;
FIG. 2A is a scanning electron micrograph of freshly prepared MXene without cysteine molecular modification in example 1 of the present invention;
FIG. 2B is a scanning electron micrograph of MXene without cysteine modification in example 1 of the present invention after standing at room temperature for 2 weeks.
Fig. 3 is a graph showing the electromagnetic shielding performance of the MXene film modified with the fresh cysteine molecule and the MXene film modified with the cysteine molecule after being left for 2 weeks according to example 1 of the present invention.
Fig. 4 is a graph of the electromagnetic shielding performance of a freshly made MXene film and a MXene film made after 2 weeks standing in example 1 of the present invention.
Fig. 5 is a graph of the mechanical properties of the MXene film modified with cysteine molecules prepared in example 1 of the present invention.
Detailed Description
The following examples are only a part of the present invention, and not all of them. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, belong to the protection scope of the invention.
In the present invention, all the equipment, materials and the like are commercially available or commonly used in the industry, if not specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
MXene was modified with cysteine molecules in this example as follows:
preparing 240 ml of cysteine aqueous solution with the concentration of 0.1mol per liter as sample treatment fluid;
stripping multilayer and single-layer MXene nanosheets by a liquid phase stripping method and transferring the MXene nanosheets into a glass bottle to obtain an MXene sample to be treated; wherein, the liquid phase stripping method comprises the following steps: 2gMAX phase Ti 3 AlC 2 Slowly adding the powder into an etchant solution prepared by dissolving 2g of LiF in 40mL of 9M HCl solution, and stirring for 24-48 h at 35 ℃; washing with deionized water, centrifuging at 3500rpm, discarding supernatant, washing repeatedly, and centrifuging until pH is not less than 6; then, dispersing the obtained precipitate in deionized water under the protection of Ar gas, oscillating for 5-60 minutes by a vortex mixer, centrifuging for 5 minutes at 3500rpm, and collecting Ti 3 C 2 T x An MXene nanosheet sample;
taking Ti 3 C 2 T x Dispersing an MXene nanosheet sample in deionized water, adding the sample treatment liquid, and adding Ti into the final mixed liquid 3 C 2 T x Concentration of MXene nanosheetThe concentration of 0.1mg/mL and the concentration of cysteine are 0.1mol/L, and the aqueous solution containing MXene modified by cysteine molecules is obtained after mixing and standing for 1 day.
The MXene sample modified with cysteine molecules was stored at room temperature, observed for signs of oxidation within 2 weeks and compared with MXene samples not modified with cysteine molecules:
fig. 1A and fig. 1B show the scanning electron micrographs of the MXene sample modified by the cysteine molecule prepared in this example and the MXene sample after being left at room temperature for two weeks, and it can be seen that the MXene modified by the cysteine molecule prepared in this example has no sign of any oxidation on the surface after being left at room temperature for 2 weeks. Therefore, the preparation method provided by the embodiment can improve the antioxidant capacity of MXene by using the modification of cysteine molecules, and can keep the stability of MXene structure and performance in aqueous solution.
Fig. 2A and 2B show scanning electron micrographs of a fresh MXene sample without cysteine modification prepared by liquid phase exfoliation and after 2 weeks at room temperature, respectively, from which it can be seen that after two weeks, the surface of the MXene sample showed significant oxidation, compared to the sample prepared immediately.
In this embodiment, the uniformly mixed and standing aqueous solution is vacuum filtered to form a film, so as to obtain an MXene film modified by cysteine molecules, and the relevant performance of the MXene film is tested, and the process is as follows:
newly prepared cysteine modified MXene aqueous solution and the aqueous solution after being placed for 2 weeks are subjected to suction filtration to form films, the electromagnetic shielding performance of the films is respectively tested, a Keysight PNA-E5227B vector network analyzer is used for testing the electromagnetic shielding performance of the films, S parameters (S11 and S21) are acquired in an X-band frequency range (8.2-12.4 GHz) by the Keysight & N5227B vector network analyzer, EMISE, A, R and T are calculated from the S parameters by using the following formula, and the test result is shown in figure 3.
R＝|S 11 | 2 T＝|S 21 | 2 Electromagnetic wave absorption coefficient a: a = 1-R-T
Reflection efficiency SE R ：SE R ＝﹣10lg(1-R)
Absorption efficiency SE A ：
Shielding effectiveness EMISE: SE T ＝SE R +SE A
This example also measured the electromagnetic shielding performance of a fresh MXene sample from a liquid phase stripping process without cysteine modification and a MXene film suction filtered after standing at room temperature for 2 weeks as described above and the results are shown in FIG. 4.
As can be seen from fig. 3 and 4, the MXene film electromagnetic shielding performance modified by cysteine molecules prepared in this embodiment is not only superior to that of the MXene film without cysteine molecule modification, but also has good stability in air, and after being placed for 2 weeks, the electromagnetic shielding performance of the MXene film without cysteine molecule modification can be well maintained and is not substantially reduced, and the electromagnetic shielding performance of the MXene film without cysteine molecule modification is significantly reduced, so that the modification method provided by the present invention lays a foundation for the application of the MXene material in electromagnetic shielding.
The mechanical property of the MXene film modified by the cysteine molecules is also tested, and the tensile test shows that the mechanical property of the MXene material can be greatly improved by modifying the cysteine molecules.
Example 2
MXene was modified with histidine in this example as follows:
preparing 240 ml of histidine aqueous solution with the concentration of 0.1mol per liter as sample treatment solution;
stripping multilayer and single-layer MXene nanosheets by a liquid phase stripping method and transferring the MXene nanosheets into a glass bottle to obtain an MXene sample to be treated; the procedure of the liquid phase stripping method was the same as in example 1;
taking Ti 3 C 2 T x Dispersing an MXene nanosheet sample in deionized water, adding the sample treatment liquid, and adding Ti into the final mixed liquid 3 C 2 T x The concentration of MXene nano-sheet is 0.1mg/mL, the concentration of histidine is 0.1mol/L, and the mixture is evenly mixedStanding for 24h to obtain MXene modified by histidine molecules.
Example 3
MXene was modified with alanine molecules in this example as follows:
preparing 240 ml of alanine aqueous solution with the concentration of 0.1mol per liter as sample treatment liquid;
stripping multilayer and single-layer MXene nanosheets by a liquid phase stripping method and transferring the MXene nanosheets into a glass bottle to obtain an MXene sample to be treated; the procedure of the liquid phase stripping method was the same as in example 1;
taking Ti 3 C 2 T x Dispersing an MXene nanosheet sample in deionized water, adding the sample treatment liquid, and adding Ti into the final mixed liquid 3 C 2 T x The concentration of the MXene nano-sheet is 0.1mg/mL, the concentration of alanine is 0.1mol/L, and the MXene modified by the alanine molecule is obtained after mixing uniformly and standing for 24h.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A method for modifying MXene, wherein the MXene is modified by an amino acid; the method for modifying MXene comprises the following steps:
mixing MXene nanosheets and amino acid molecules in a solution to react, and finishing modification.
2. The method of claim 1, wherein the mixing reaction of MXene nanosheets and amino acid molecules in solution completes the modification for 24 hours or more.
3. The method of claim 1, wherein 0.01 to 0.03mol of amino acid is present per 0.1g of MXene nanoplatelets in the solution;
preferably, the concentration of the amino acid molecules in the solution is 0.01 mol/L-0.3 mol/L.
4. The method of claim 1, wherein the MXene nanoplatelets are selected from at least one of multilayer MXene nanoplatelets and monolayer MXene nanoplatelets.
5. The method of claim 1, wherein the MXene is Ti 3 C 2 T x 。
6. The method of claim 5, wherein the Ti is 3 C 2 T x Prepared by a liquid phase stripping method or a molten salt method;
preferably, the liquid phase lift-off process is by etching MAX phase Ti 3 AlC 2 The powder specifically comprises the following steps:
subjecting the MAX phase Ti 3 AlC 2 Adding the powder into an etchant solution, stirring for 24-48 h, and centrifugally washing until the pH value is more than or equal to 6;
preferably, the etchant solution is a solution obtained by dissolving LiF in hydrochloric acid.
7. The method of claim 1, wherein the amino acid molecule is selected from at least one of alanine, glycine, lysine, glutamic acid, arginine, histidine, and cysteine.
8. MXene modified with an amino acid molecule obtained by the method of any one of claims 1 to 7.
9. An amino acid molecule-modified MXene film prepared from the amino acid molecule-modified MXene of claim 8.
10. Use of the MXene film modified with the amino acid molecule of claim 9 in the preparation of electromagnetic shielding materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116239932A (en) * | 2023-02-15 | 2023-06-09 | 西南交通大学 | Gly@Ti-based 3 C 2 Tx/AgNWs high-conductivity water-based paint and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698847A (en) * | 2019-10-21 | 2020-01-17 | 西北工业大学 | Waterborne polyurethane-MXene electromagnetic shielding bionic nano composite material film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698847A (en) * | 2019-10-21 | 2020-01-17 | 西北工业大学 | Waterborne polyurethane-MXene electromagnetic shielding bionic nano composite material film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SIHAO LI等: "Reinforced anticorrosion performance of waterborne epoxy coating with eco-friendly L-cysteine modified Ti3C2Tx MXene nanosheets", vol. 161, pages 2 * |
| 蔡木易: "《食源性低聚肽》", vol. 1, 中国轻工业出版社, pages: 92 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116239932A (en) * | 2023-02-15 | 2023-06-09 | 西南交通大学 | Gly@Ti-based 3 C 2 Tx/AgNWs high-conductivity water-based paint and preparation method thereof |
| CN116239932B (en) * | 2023-02-15 | 2023-12-12 | 西南交通大学 | Gly@Ti-based 3 C 2 Tx/AgNWs high-conductivity water-based paint and preparation method thereof |
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