CN114011261B - General method for enhancing stability of MXene aqueous solution - Google Patents
General method for enhancing stability of MXene aqueous solution Download PDFInfo
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Abstract
The invention provides a general method for enhancing stability of MXene aqueous solution, and belongs to the field of materials. The inorganic salt which is cheap and easy to obtain is used for synchronously reducing the proportion of free water molecules and the concentration of dissolved oxygen in water, the stability of MXene in the aqueous solution is improved, and the storage time of the MXene aqueous solution is obviously prolonged. The used inorganic salt protective agent can be efficiently recovered by a simple and easy evaporation crystallization method. The method provided by the invention can realize stable storage of MXene aqueous solution for up to 400 days, and solves the fundamental problems disturbing MXene production and processing, long-term storage and transportation and practical application. The synthesis method is environment-friendly, low in energy consumption, easy to control and universal, and can be used for large-scale production.
Description
Technical Field
The invention belongs to the field of materials, and relates to a general method for enhancing stability of MXene aqueous solution.
Background
MXene is a novel two-dimensional crystal of transition metal carbide or nitride obtained by acid etching of MAX phase of layered ceramic material. The chemical formula is M n+1 X n T x Wherein M is n+1 X n Represents a transition metal carbonitride structural skeleton (M is a transition metal element, X is carbon or a nitrogen element, and n is 1, 2 or 3), T x Indicating its surface chemical functional groups (e.g., -OH, -F, -O, etc.). The material has a two-dimensional structure similar to graphene and excellent electrical, mechanical and magnetic properties. In recent years, the material is widely applied to the wide fields of energy storage, catalysis, electromagnetic shielding, water treatment, gas/biological sensing, biological medical treatment, photoelectric devices and the like, and is considered as a new two-dimensional material with machine and tool prospects.
The unique performance is endowed by the two-dimensional nanostructure of MXene, but the etching synthesis of MXene exposes a large amount of metastable metal atoms and high-reactivity defect sites on the surface of MXene, so that MXene is extremely easy to oxidize and deteriorate in aqueous solution, the two-dimensional structure is collapsed, the physical and chemical properties are damaged, and the production, processing, long-term storage and transportation and practical application of MXene are greatly limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a general method for enhancing the stability of MXene aqueous solution, which utilizes cheap and easily available inorganic salt to synchronously reduce the proportion of free water molecules and the concentration of dissolved oxygen in water and improve the stability of MXene in the aqueous solution, thereby greatly prolonging the storage time of the MXene aqueous solution to 30-400 days. The basic problems which disturb MXene production and processing, long-term storage and transportation and actual application are solved. The synthesis method is 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 invention adopts the following technical scheme:
a general method for enhancing stability of MXene aqueous solution is characterized in that inorganic salt which is cheap and easy to obtain is dissolved in the MXene aqueous solution at room temperature, and after the inorganic salt is added in a room temperature environment, water activity and dissolved oxygen concentration in the MXene aqueous solution can be synchronously reduced to form the MXene aqueous solution which is stable for a long time, and further storage life of MXene in the aqueous solution is remarkably prolonged. Wherein, the adjustment of water activity (proportion of free water molecules) can be realized by adjusting the type and concentration of inorganic salt in MXene aqueous solution, and the minimum value can be reduced to 0.11.
The inorganic salt is NaCl, LiCl and K 2 SO 4 ，CaCl 2 ，ZnCl 2 NaBr, NaF and the like.
The concentration range of the inorganic salt is 0.6M-11M.
The structural general formula of MXene is M n+1 X n Wherein M represents one or more of Ti, Nb, V, Mo, Zr, Cr, W and Ta, X represents one or two of C or N, and N is 1, 2 and 3.
The concentration range of the MXene aqueous solution is 1g L –1 -15g L –1 。
The water activity after reduction in the aqueous MXene solution ranged less than 1.00.
When in use, pure MXene can be obtained after washing to remove inorganic salt, and in addition, the inorganic salt solution with MXene filtered out is evaporated and crystallized at a certain temperature, so that the recovery of the inorganic salt can be realized.
The invention solves the problem that MXene is easy to oxidize and deteriorate in aqueous solution, and solves the fundamental problems which puzzle MXene production and processing, long-term storage and transportation and practical application. The method has the following beneficial effects:
(1) the invention provides a general method for enhancing the stability of MXene aqueous solution, which can realize that the physical and chemical properties of MXene can be efficiently maintained after long-term storage in the aqueous solution;
(2) the invention uses recyclable and reusable cheap inorganic salt as the protective agent, has green and environment-friendly process, is easy for large-scale production, has good economical efficiency and is suitable for large-scale application.
(3) The invention realizes the high-efficiency protection of MXene by reducing the water activity and the dissolved oxygen concentration of the aqueous solution by using inorganic salt, is fundamentally different from the conventional MXene protection technologies of using a reducing protective agent, an adsorptive protective agent, surface coating, freezing and the like in principle, and greatly reduces the process complexity and the cost.
Drawings
FIG. 1 is Ti after 30 days of NaCl protection according to example 1 of the present invention 3 C 2 Scanning electron microscope photographs of MXene;
FIG. 2 is Ti after 60 days of NaCl protection according to example 2 of the present invention 3 C 2 X-ray diffraction pattern of MXene;
FIG. 3 shows CaCl according to example 4 of the invention 2 Ti after 180 days of protection 3 C 2 Scanning electron microscope photographs of MXene;
FIG. 4 is Ti after 400 days of LiCl protection as described in example 5 of the present invention 3 C 2 Transmission electron micrograph of MXene;
FIG. 5 is V after 280 days of LiCl protection as described in example 6 of the present invention 4 C 3 Scanning electron micrograph of MXene.
Detailed Description
Aiming at the bottleneck problem of MXene application and a plurality of defects of the prior art, the inventor of the present invention provides the technical scheme of the present invention through long-term research and a large amount of practice, and further explains the technical scheme, the implementation process and the principle thereof, 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.
Example 1
1) NaCl was homogeneously dissolved in 200mL of Ti 3 C 2 MXene aqueous solution, NaCl concentration 3M, Ti used 3 C 2 MXene aqueous solution concentration of 15g L –1 。
2) Placing the MXene aqueous solution containing inorganic salt in room temperature environment to form long-term stable MXene aqueous solution, wherein the water activity is 0.92, and the dissolved oxygen concentration is 3.67mg L -1 .
3) Filtering, washing and removing NaCl to obtain pure Ti 3 C 2 MXene。
4) The NaCl which is filtered to remove MXene is evaporated and crystallized at the temperature of 55 ℃, so that the recovery of NaCl can be realized.
As shown in FIG. 1, Ti was obtained after 30 days of storage under the above-mentioned conditions 3 C 2 MXene still keeps its two-dimensional structure, proves its good protection effect.
Example 2
1) NaCl was homogeneously dissolved in 200mL of Ti 3 C 2 MXene aqueous solution with NaCl concentration of 5.5M and Ti used 3 C 2 MXene aqueous solution concentration of 1g L –1 。
2) Placing the MXene aqueous solution containing inorganic salt in room temperature environment to form long-term stable MXene aqueous solution, wherein the water activity is 0.76, and the dissolved oxygen concentration is 1.95mg L -1
3) Filtering, washing and removing NaCl to obtain pure Ti 3 C 2 MXene。
4) The NaCl which is filtered to remove MXene is evaporated and crystallized at the temperature of 55 ℃, so that the recovery of NaCl can be realized.
As shown in fig. 2, the aboveAfter 30 days of storage under the conditions, Ti 3 C 2 The X-ray diffraction pattern of MXene has no obvious change, and the crystal structure is well maintained.
Example 3
1) Will K 2 SO 4 Uniformly dissolved in 200mL of Ti 3 C 2 MXene in aqueous solution, wherein K 2 SO 4 At a concentration of 0.6M, Ti is used 3 C 2 The concentration of MXene aqueous solution is 10g L –1 。
2) The MXene aqueous solution containing the inorganic salt is placed in a room temperature environment to form the MXene aqueous solution with long-term stability, wherein the water activity is 0.96.
3) After filtration, washing and removal of K 2 SO 4 Pure Ti can be obtained 3 C 2 MXene。
4) K to be filtered off MXene 2 SO 4 The solution is evaporated and crystallized at 55 ℃ to realize K 2 SO 4 And (4) recovering.
Example 4
1) Adding CaCl 2 Uniformly dissolved in 200mL of Ti 3 C 2 MXene aqueous solution, wherein CaCl is contained 2 At a concentration of 6M, Ti is used 3 C 2 MXene aqueous solution with concentration of 6g L –1 。
2) The MXene aqueous solution containing the inorganic salt is placed in a room temperature environment to form the MXene aqueous solution with long-term stability, wherein the water activity is 0.36.
3) Filtering and washing to remove CaCl 2 Then pure Ti is obtained 3 C 2 MXene。
4) Filtering MXene-removed CaCl 2 Evaporating and crystallizing at 200 deg.C to obtain CaCl 2 And (4) recovering.
As shown in FIG. 3, Ti was obtained after storage for 180 days under the above-mentioned conditions 3 C 2 Scanning electron micrographs of MXene showed good retention of its two-dimensional structure.
Example 5
1) LiCl was uniformly dissolved in 200mL of Ti 3 C 2 MXene aqueous solution with LiCl concentration of 11M and Ti 3 C 2 The concentration of MXene aqueous solution is 10g L –1 。
2) The MXene aqueous solution containing the inorganic salt is placed in a room temperature environment to form the MXene aqueous solution with long-term stability, wherein the water activity is 0.11.
3) After LiCl is removed by filtration and washing, pure Ti can be obtained 3 C 2 MXene。
4) The LiCl of which MXene is filtered out is evaporated and crystallized at 98 ℃, so that the LiCl can be recovered.
As shown in FIG. 4, Ti after storage for 400 days under the above-mentioned conditions 3 C 2 The transmission electron microscope photo of MXene shows that the shape of the two-dimensional nanosheet is still maintained, and the good protection effect of the method is shown.
Example 6
1) LiCl was uniformly dissolved in 20mL of V 4 C 3 MXene aqueous solution with LiCl concentration of 11M and V 4 C 3 MXene aqueous solution concentration of 1g L –1 。
2) The MXene aqueous solution containing the inorganic salt is placed in a room temperature environment to form the MXene aqueous solution with long-term stability, wherein the water activity is 0.11.
3) After LiCl is removed by filtration and washing, pure V can be obtained 4 C 3 MXene。
4) The LiCl of which MXene is filtered out is evaporated and crystallized at 98 ℃, so that the LiCl can be recovered.
As shown in FIG. 5, V after 30 days of storage under the above conditions 4 C 3 Scanning electron micrographs of MXene showed good retention of its two-dimensional structure.
Example 7
1) Uniformly dissolving NaBr in 200mL of Ti 3 C 2 In MXene aqueous solution, the NaBr concentration is 6M, Ti is used 3 C 2 MXene aqueous solution concentration of 1g L –1 。
2) The MXene aqueous solution containing the inorganic salt is placed in a room temperature environment to form the MXene aqueous solution with long-term stability, wherein the water activity is 0.65.
3) After filtering and washing to remove NaBr, i.e.Pure Ti can be obtained 3 C 2 MXene。
4) The NaBr filtered from MXene is evaporated and crystallized at 110 ℃, so that the recovery of NaBr can be realized.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which 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 variations made in accordance with the spirit of the present invention are intended to be covered by the scope of the present invention.
Claims (3)
1. A general method for enhancing stability of MXene aqueous solution is characterized by comprising the following specific steps: dissolving inorganic salt in MXene aqueous solution at room temperature, and adding the inorganic salt to synchronously reduce the water activity and dissolved oxygen concentration in the MXene aqueous solution to form long-term stable MXene aqueous solution, thereby obviously prolonging the storage life of MXene in the aqueous solution; the concentration range of the inorganic salt is 0.6M-11M; the concentration range of the MXene aqueous solution is 1g L –1 -15g L –1 (ii) a The water activity range of the MXene aqueous solution after reduction is less than 1.00.
2. The general method for enhancing stability of MXene aqueous solution according to claim 1, wherein the inorganic salt is NaCl, LiCl, K 2 SO 4 ，CaCl 2 ，ZnCl 2 ，NaBr，NaF。
3. The general method for enhancing the stability of MXene aqueous solution according to claim 1, wherein the general structural formula of MXene is M n+1 X n Wherein M represents one or more of Ti, Nb, V, Mo, Zr, Cr, W and Ta, X represents one or two of C or N, and N is 1, 2 and 3.
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Citations (5)
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| CN110038634A (en) * | 2019-05-07 | 2019-07-23 | 大连理工大学 | A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction |
| WO2020252304A1 (en) * | 2019-06-13 | 2020-12-17 | Drexel University | EDGE CAPPING OF 2D-MXene SHEETS WITH POLYANIONIC SALTS TO MIGITATE OXIDATION IN AQUEOUS COLLOIDAL SUSPENSIONS |
| CN112499601A (en) * | 2020-12-15 | 2021-03-16 | 江苏师范大学 | Method for efficiently preparing thin-layer MXene |
| WO2021167747A2 (en) * | 2020-01-24 | 2021-08-26 | Drexel University | Synthesis of mxene suspensions with improved stability |
| WO2021177551A1 (en) * | 2020-03-04 | 2021-09-10 | 한국과학기술원 | Method for improving oxidation stability of mxene through control of surface functional group |
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| CN110038634A (en) * | 2019-05-07 | 2019-07-23 | 大连理工大学 | A kind of oxygen evolution reaction catalysts and its synthetic method based on MXene Yu metal organic framework compound composite construction |
| WO2020252304A1 (en) * | 2019-06-13 | 2020-12-17 | Drexel University | EDGE CAPPING OF 2D-MXene SHEETS WITH POLYANIONIC SALTS TO MIGITATE OXIDATION IN AQUEOUS COLLOIDAL SUSPENSIONS |
| WO2021167747A2 (en) * | 2020-01-24 | 2021-08-26 | Drexel University | Synthesis of mxene suspensions with improved stability |
| WO2021177551A1 (en) * | 2020-03-04 | 2021-09-10 | 한국과학기술원 | Method for improving oxidation stability of mxene through control of surface functional group |
| CN112499601A (en) * | 2020-12-15 | 2021-03-16 | 江苏师范大学 | Method for efficiently preparing thin-layer MXene |
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| 《二维材料MXenes 稳定性研究进展》;刘兴民等;《沈阳航空航天大学学报》;20210831;第38卷(第4期);第9-15页 * |
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