CN111704137B - Preparation method of high-yield low-fluorine-content few-layer MXenes nanosheet - Google Patents
Preparation method of high-yield low-fluorine-content few-layer MXenes nanosheet Download PDFInfo
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Abstract
A preparation method of a few-layer MXenes nanosheet with high yield and low fluorine content belongs to the technical field of nano materials. Mixing organic matters containing hydroxyl or active oxygen such as polyethylene glycol or alkylphenol polyoxyethylene, MAX, hydrochloric acid and lithium fluoride, stirring at 35 ℃ for 24 hours, washing with water until PH is neutral, and centrifuging to obtain the low-fluorine-content MXenes nanosheet. The invention effectively solves a series of problems of low yield and high fluorine content in the preparation process of the few-layer MXenes nanosheets, and has the advantages of simple preparation method, low price, large-scale production and practical prospect.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a high-yield low-fluorine-content few-layer MXenes nanosheet.
Background
The transition metal carbide MXenes is a novel two-dimensional material with a graphene-like structure, and has the advantages of good chemical stability, hydrophilicity, conductivity, mechanical property, high specific surface area and the like. Since the discovery of the Yury GogotSi and the like in 2011, the method has shown great application prospects in the fields of electrochemical energy storage, sewage treatment, sensors, seawater desalination and the like. At present, the MXenes preparation method is mainly obtained by etching weak A-site elements in MAX phase through hydrofluoric acid or a mixed solution of villiaumite and hydrochloric acid. MXenes materials prepared by the method often have functional groups such as F, OH, O and the like, and the yield of the MXenes nanosheets prepared by stripping is extremely low. More seriously, the application of MXenes nanosheets, especially in electrochemical energy storage, is hindered by the presence of a large number of F functional groups. Therefore, the exploration of a method for preparing MXenes nanosheets with high yield and low fluorine content through improving chemical etching is the key of further industrial application of the method.
Disclosure of Invention
The invention aims to: the method provides a simple and improved process for preparing the low-fluorine-content few-layer MXenes nanosheet, and improves the yield of the low-layer MXenes, so as to solve the problems of high fluorine content and low yield of the MXenes nanosheet in the conventional preparation method.
The method comprises the steps of mixing organic matters containing hydroxyl or active oxygen such as polyethylene glycol or alkylphenol ethoxylates, MAX, hydrochloric acid and lithium fluoride, stirring at 35 ℃ for 24 hours, washing with water until the PH is neutral, and centrifuging to obtain the low-fluorine-content MXenes nanosheet. In the stirring and etching process, a large amount of hydroxyl or active oxygen on the molecular chain of organic matter containing hydroxyl or active oxygen, such as polyethylene glycol or alkylphenol polyoxyethylene can be rapidly combined with Ti atoms to form a stable structure, so that the possibility of combining F atoms with titanium is reduced, and further, the preparation of the MXenes nanosheets with low fluorine content is realized. In addition, organic molecules containing hydroxyl or active oxygen, such as long-chain polyethylene glycol or alkylphenol ethoxylates, are also used as an intercalating agent between MXenes lamellae, so that the van der Waals force between the lamellae is reduced, the peeling speed of the lamellae is accelerated, and the yield is improved.
The specific preparation process comprises the following steps:
(1) Mixing organic substance containing hydroxyl or active oxygen such as polyethylene glycol or alkylphenol polyoxyethylene, hydrochloric acid, and lithium fluoride
Wherein, the proportion of organic matters containing hydroxyl or active oxygen such as polyethylene glycol or alkylphenol polyoxyethylene in the mixed solvent is 1-5%;
(2) Adding MAX into the mixed solution obtained in the step (1) slowly, and stirring for 24 hours at 35 ℃;
(3) Mechanically shaking the product obtained in the step (2) for 20-60min, then washing with water until the pH value is neutral, and centrifuging to obtain the low-fluorine-content few-layer MXenes nanosheet.
Wherein the organic matter containing hydroxyl or active oxygen accounts for 1-5wt% of the mixed solvent.
The specifications of the alkylphenol polyoxyethylene ether in the invention comprise OP-4, OP-7, OP-10 or OP-15, and the molecular formula is C 34 H 62 O 11 。
The invention effectively solves a series of problems of low yield and high fluorine content in the preparation process of the few-layer MXenes nanosheets, and has the advantages of simple preparation method, low price, large-scale production and practical prospect.
Drawings
FIG. 1 is a scanning electron micrograph of few-layered MXenes nanoplatelets prepared in example 1.
Figure 2 is an XRD of the few-layer MXenes nanoplates prepared in example 1.
Figure 3 is a comparison of the F content of few-layered MXenes nanoplates prepared in example 1 with a conventional sample.
Fig. 4 is a comparison of the yield of few-layered MXenes nanoplatelets prepared in example 1 to a conventional sample.
Detailed Description
Example 1:
(1) Adding 1g of polyethylene glycol and 1g of lithium fluoride into 20ml of 9M hydrochloric acid, and uniformly mixing;
(2) MAX with the mass of 1g is slowly added to the mixed solution obtained in the step (1), and stirred at the temperature of 35 ℃ for 24 hours.
(3) Mechanically shaking the product obtained in the step (2) for 20-60min, then washing with water until the pH value is neutral, and centrifuging to obtain the low-fluorine-content few-layer MXenes nanosheet.
Example 2:
(1) Adding 1gOP-4 and 1g of lithium fluoride into 20ml of 9M hydrochloric acid, and uniformly mixing;
(2) MAX with the mass of 1g is slowly added to the mixed solution obtained in the step (1), and stirred at the temperature of 35 ℃ for 24 hours.
(3) Mechanically shaking the product obtained in the step (2) for 20-60min, then washing with water until the pH value is neutral, and centrifuging to obtain the low-fluorine-content few-layer MXenes nanosheet.
Example 3:
(1) Adding 1gOP-10 and 1g of lithium fluoride into 20ml of 9M hydrochloric acid, and uniformly mixing;
(2) MAX with the mass of 1g is slowly added to the mixed solution obtained in the step (1), and stirred at the temperature of 35 ℃ for 24 hours.
(3) Mechanically oscillating the product obtained in the step (2) for 20-60min, then washing with water until the pH value is neutral, and centrifuging to obtain the low-fluorine-content few-layer MXenes nanosheet.
Comparative example 1
(1) Adding 1g of lithium fluoride into 20ml of 9M hydrochloric acid, and uniformly mixing;
(2) MAX with the mass of 1g is slowly added to the mixed solution obtained in the step (1), and is stirred at the temperature of 35 ℃ for 24 hours.
(3) Mechanically oscillating the product obtained in the step (2) for 20-60min, then washing with water until the pH value is neutral, and centrifuging to obtain the low-fluorine-content few-layer MXenes nanosheet.
SEM, XRD and XPS tests are carried out on the obtained few-layer MXenes with low fluorine content, and the few-layer MXenes nanosheets prepared by the SEM and XRD result improving process are not different from samples prepared by the conventional process, as shown in figures 1 and 2. However, XPS test shows that the fluorine content of the sample obtained by the improved process is obviously reduced, and the yield is greatly improved, as shown in figures 3 and 4.
Claims (2)
1. A preparation method of a few-layer MXenes nanosheet with high yield and low fluorine content is characterized by comprising the following steps: the preparation method comprises the following steps of,
(1) Mixing an organic matter containing hydroxyl or active oxygen, hydrochloric acid and lithium fluoride;
(2) Adding MAX into the mixed solution obtained in the step (1) slowly, and stirring for 24 hours at 35 ℃;
(3) Mechanically shaking the product obtained in the step (2) for 20-60min, then washing with water until the pH value is neutral, and centrifuging to obtain a few-layer MXenes nanosheet with low fluorine content;
wherein: the organic matter containing hydroxyl or active oxygen in the step (1) is polyethylene glycol, OP-4, OP-7, OP-10 or OP-15.
2. The method for preparing the high-yield low-fluorine-content few-layer MXenes nanosheets of claim 1, wherein: the organic matter containing hydroxyl or active oxygen accounts for 1-5wt% of the mixed solvent.
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| CN109666964B (en) * | 2019-01-16 | 2020-11-24 | 华南理工大学 | Method for rapidly preparing two-dimensional MXene film through electrophoretic deposition |
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