CN114956084A - Preparation method of Al-doped MXene - Google Patents
Preparation method of Al-doped MXene Download PDFInfo
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- CN114956084A CN114956084A CN202110215742.6A CN202110215742A CN114956084A CN 114956084 A CN114956084 A CN 114956084A CN 202110215742 A CN202110215742 A CN 202110215742A CN 114956084 A CN114956084 A CN 114956084A
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Abstract
The invention discloses a preparation method of Al-doped MXene, and belongs to the technical field of two-dimensional nano materials. In the method, M is firstly n+1 AlX n And with AlCl 3 And (2) calcining a NaCl-KCl molten salt system at a low temperature, carrying out element replacement on the A phase of the MAX to synthesize an excessive Al-doped nano laminar MAX phase, and then etching and extracting the A metal atomic layer in the MAX phase material by a chemical etching method to prepare the two-dimensional laminar nano material MXene. The MXene prepared by the method has obviously improved oxidation resistance, and the problem that the MXene can be quickly oxidized in an aqueous solution is solved.
Description
Technical Field
The invention belongs to the technical field of two-dimensional nano materials, and particularly relates to a preparation method of Al-doped MXene.
Background
With the expansion of the research scope of MXene, research on improving the performance of MXene by exploring new synthesis routes and processing methods to improve the quality of MXene is continuously developing. However, MXene is rapidly oxidized in aqueous solution and is generally stored in aqueous media for no more than a few consecutive weeks. Here we have modified the MAX phase precursor to solve the problem of rapid oxidation of MXene in aqueous solution. In order not to introduce impurities which are not easy to remove, the MAX phase precursor is improved by an aluminum liquid soaking method, and excessive aluminum can cause M with improved stoichiometry and crystallinity n+1 AlX n The MXene prepared by the method has obviously improved oxidation resistance, and the storage time of the aqueous solution of the MXene and the stability of the MXene are prolonged.
Yur of Drisel universityThe y Gogotsi team is entitled "Modified MAX Phase Synthesis for environmental Stable and high purity Conductive Ti 3 C 2 MXene "reports the preparation of Ti containing a small amount of Al impurities by controlling the ratio of TiC, Ti and Al powders 3 AlC 2 Precursor, stable Ti obtained by HF etching 3 C 2 MXene. The literature indicates that in Ti 3 AlC 2 The inclusion of excess aluminium during the synthesis of the MAX phase precursor leads to Ti with improved stoichiometry and crystallinity 3 AlC 2 And (4) generation of crystal grains. And made of modified Ti 3 AlC 2 Produced Ti 3 C 2 The nano-sheet has obviously improved oxidation resistance. In the MAX phase Ti 3 AlC 2 The high-temperature synthesis of (2) is carried out with an excess of aluminum (element a) added to form a liquid phase at an early stage of the sintering process, and the presence of molten metal during the sintering reaction promotes the diffusion of the reactants, resulting in Ti 3 AlC 2 The grains have improved structural order and morphology. Thereby eliminating Ti 3 C 2 Ti caused by defects generated during the synthesis of 3 C 2 High instability in aqueous solutions and air.
The Ningbo material technology of Chinese academy of sciences and the yellow celebration team of engineering research reported that various MXenes can be synthesized by melting a MAX phase and a non-conventional MAX phase precursor of Si, Zn and Ga through a displacement reaction between a MAX phase and a late transition metal halide in an article entitled "A general Lewis acid etching solution for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte".
In addition, the Huangqing team discloses an MXene material with Cl as a surface group and a preparation method and application thereof in Chinese patent with application publication No. CN 109437177A, and the key point is to mix a precursor MAX phase material and a transition metal chloride and perform high-temperature reaction to obtain the MXene material with Cl as the surface group.
Shanghai university discloses an i-MAX phase material with a core-shell structure and a preparation method thereof in Chinese patent with application publication number CN 112225221A, and the key point is to select CuCl 2 Salt is used as an etching agent, and the transition metal carbide with a shell layer having a mesoporous structure and a core layer still having an i-MAX phase brand new core-shell structure are obtained by high-temperature calcination.
Thus, the reaction mechanism can be changed in AlCl through a replacement reaction 3 Pair M in molten salt system n+1 AlX n Doping the precursor with Al as an A-site element, and obtaining the MAX phase with excessive aluminum doping by a low-temperature calcination method. Excess aluminum (element a) is added during the calcination process to form a liquid phase at an early stage of the sintering process, and the presence of molten metal during the sintering reaction promotes the diffusion of the reactants, resulting in M n+1 AlX n The grains have improved structural order and morphology. Thus eliminating the defects generated during the synthesis of MXene, which lead to its high instability in aqueous solutions and in air. The AlCl provided by the invention 3 The MXene prepared by the method of doping excessive aluminum in the molten salt system has better oxidation resistance, thereby obviously improving the storage life and the chemical stability of the MXene and providing simplicity for the study of the MXene; in addition, the method has low calcination temperature and controllable process, belongs to a preparation method with low energy consumption, and has strong popularization and application values.
Disclosure of Invention
The invention aims to provide a preparation method of Al-doped MXene. The method of the invention is realized by AlCl in the calcining process 3 The molten salt system improves the MAX phase to obtain M doped with excessive Al n+1 AlX n Phase (1); and obtaining the antioxidant MXene colloidal solution by chemical etching, intercalation and repeated centrifugation.
In order to achieve the purpose, the technical scheme of the invention comprises the following steps:
step 1: m n+1 AlX n And phase with AlCl 3 Fully grinding the mixture of NaCl and KCl, uniformly mixing, filling into an alumina crucible, covering with a graphite foil, and putting into a tube furnace;
step 2: calcining the mixture under an inert atmosphere;
and 3, step 3: cooling to room temperature, grinding the sintered block, and fully washing with HCl until no bubbles escape;
and 4, step 4: filtering with a vacuum filtration device, and repeatedly filtering with deionized water;
and 6: vacuum drying and screening to obtain an excessive Al-doped MAX phase;
and 7: and etching the MAX phase doped with excessive Al, wherein the etching method comprises the following steps.
I, etching MAX phase material by lithium fluoride and hydrochloric acid
Adding the MAX phase material into a mixed solution of lithium fluoride and hydrochloric acid, reacting, taking a precipitate, washing and centrifuging the precipitate alternately until the pH value of a washing solution is more than 6, and drying to obtain the single-layer MXene material.
II, HF etching MAX phase material
Mixing the improved MAX phase raw material with HCl, deionized water and HF mixture, stirring overnight, centrifuging and washing to obtain multilayer deposit, then intercalating in LiCl solution, and repeatedly centrifuging and washing with deionized water to obtain the monolayer MXene material.
III, etching MAX phase material by molten salt method
MAX phase raw materials, chloride ion salts or bromide ion salts, NaCl and KCl are weighed and placed into ball milling equipment to be fully ball-milled and mixed evenly. And then putting the ground powder into an alumina crucible, putting the alumina crucible into a tube furnace, reacting at a high temperature in an inert atmosphere, and cooling. And (3) soaking the reaction product in dilute hydrochloric acid, then ultrasonically cleaning, vibrating and standing, taking a precipitate, and repeatedly centrifugally cleaning and intercalating the precipitate by using deionized water to obtain the single-layer MXene material.
IV, NaOH assisted hydrothermal method for etching MAX phase material
MXene powder with the purity of 92 wt.% is prepared under the hydrothermal action by treating MAX phase raw material with NaOH with a certain concentration.
Preferably, M n+1 AlX n Phase to molten aluminum salt molar ratio of 1: 1-1: 8;
preferably, the calcining temperature is 50-200 ℃, and the heat preservation time is 5-24 h;
preferably, 6-12M HCl is used for washing the sintered blocks, and the washing time is more than 2 h.
Compared with the prior art, the invention has the advantages that:
（1）AlCl 3 the molten salt system enables the calcination temperature during excessive Al doping to be far lower than the temperature reported at present, the calcination temperature used in the invention is not more than 200 ℃, and the temperature of the reported Lewis molten salt is 550-750 ℃;
(2) an excess of aluminium results in M having improved stoichiometry and crystallinity n+1 AlX n The generation of crystal grains eliminates the defects generated in the synthesis process of MXene, a stable MXene colloidal solution is formed, and the improvement of the quality of monolithic MXene leads the MXene film to have higher electronic conductivity;
(3) the prepared MXene has better oxidation resistance, thereby obviously improving the storage life and the chemical stability of the MXene and providing simplicity for the study of the MXene.
Drawings
FIG. 1 shows organ-like excess Al-doped Ti 3 C 2 MXene SEM picture
FIG. 2 shows excessive Al doping of Ti 3 C 2 MXene element distribution diagram including Al, Ti, C and other elements
FIG. 3 is a schematic representation of a cross-sectional view through AlCl 3 Excess Al-doped Ti prepared by molten salt system 3 C 2 MXene and Ti prepared by traditional method 3 C 2 Graph comparing the oxidation degree of MXene in (a) powder and (b) solution in the same time.
Detailed Description
The following describes the substance of the present invention with reference to the examples.
Example 1
In this example, oxidation-resistant Ti was prepared by the following method 3 C 2 MXene:
Ti 3 AlC 2 And with AlCl 3 Fully grinding a mixture of a NaCl-KCl molten salt system, uniformly mixing, filling the mixture into an alumina crucible, covering with a graphite foil, and putting into a tubular furnace; calcining the mixture in Ar atmosphere at the calcining temperature of 150 ℃ for 10 h; cooling to room temperature, grinding the sintered block to obtain Al-Ti 3 AlC 2 Powder; washing with 9M HCl until no more bubbles remainedUntil escaping; repeatedly filtering the excessive Al-doped Ti by using a filter membrane with the aperture of 5 mu m 3 AlC 2 And a HCl mixture; then drying in a vacuum oven; sieving with 400 mesh sieve to obtain Ti doped with excessive Al 3 AlC 2 And (4) phase(s). Adding MAX phase material into mixed solution of lithium fluoride and hydrochloric acid, reacting, taking precipitate, washing and centrifuging the precipitate alternately until pH of washing solution is more than 6, and drying to obtain antioxidant Ti 3 C 2 MXene materials.
Example 2
In this example, oxidation-resistant Ti was prepared by the following method 2 C MXene:
Ti 2 AlC phase and AlCl 3 Fully grinding a mixture of a NaCl-KCl molten salt system, uniformly mixing, filling the mixture into an alumina crucible, covering with a graphite foil, and putting into a tubular furnace; calcining the mixture in Ar atmosphere at the calcining temperature of 130 ℃ for 12 h; cooling to room temperature, grinding the sintered block to obtain Al-Ti 2 AlC powder; washing with 9M HCl until no more bubbles escape; repeatedly filtering the excessive Al-doped Ti by using a filter membrane with the aperture of 5 mu m 2 AlC and HCl mixtures; then drying in a vacuum oven; sieving with 400 mesh sieve to obtain Ti doped with excessive Al 2 An AlC phase. Adding MAX phase material into mixed solution of lithium fluoride and hydrochloric acid, taking precipitate after reaction, washing and centrifuging the precipitate alternately until the pH value of washing liquid is more than 6, and drying to obtain antioxidant Ti 2 CMXene material.
Example 3
In this example, oxidation-resistant V was prepared by the following method 2 C MXene:
V 2 AlC and AlCl 3 Fully grinding a mixture of a NaCl-KCl molten salt system, uniformly mixing, filling the mixture into an alumina crucible, covering with a graphite foil, and putting into a tubular furnace; calcining the mixture in Ar atmosphere at the calcining temperature of 150 ℃ for 12 h; cooling to room temperature, grinding the sintered cake to obtain Al-V 2 AlC powder; washing with 9M HCl until no more bubbles escapeUntil the end is reached; repeatedly filtering the excessive Al-doped V by using a filter membrane with the aperture of 5 mu m 2 AlC and HCl mixtures; then drying in a vacuum oven; sieving with 400 mesh sieve to obtain V doped with excessive Al 2 An AlC phase. Adding MAX phase material into mixed solution of lithium fluoride and hydrochloric acid, reacting, taking precipitate, washing and centrifuging the precipitate alternately until pH of washing solution is more than 6, and drying to obtain antioxidant V 2 CMXene material.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. The preparation method of Al-doped MXene is characterized by comprising the following steps of n+1 AlX n Precursors and AlCl 3 Molten salt system of said AlCl 3 The molten salt system is AlCl 3 NaCl-KCl, the MAX phase comprises M with Al as the A-site element n+1 AlX n Precursor, said excess Al being in the pure phase M n+1 AlX n A small amount of impurity aluminum (namely, A site element) is introduced.
2. The method of claim 1, wherein M is n+1 AlX n Comprising Ti 3 AlC 2 、Ti 2 AlC、V 2 AlC、Nb 2 AlC、Cr 2 Any one or a combination of two or more of alcs.
3. The method of claim 1, comprising:
the M is added n+1 AlX n Precursors and said AlCl 3 Mixing the molten salt system uniformly;
calcining the obtained product in the step (1) in a tubular furnace, washing with HCl, drying and screening to obtain the excessive Al-doped MAX phase;
and (3) carrying out lamellar separation on the step (2) by a chemical etching method to obtain a single-lamellar MXene colloidal solution.
4. The method of claim 3, wherein M is present in step (1) n+1 AlX n The molar ratio of precursor to aluminum molten salt system is 1: 1-1: 8.
5. the method of claim 3, wherein the calcining at 50-200 ℃ in step (2) is carried out for 5-24 h.
6. The use of the anti-oxidation MXene material and its composite material prepared by etching according to any one of claims 1-5 in wave-absorbing or electromagnetic shielding or conductive materials or biomaterials.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114956085A (en) * | 2021-02-26 | 2022-08-30 | 苏州北科纳米科技有限公司 | Method for preparing antioxidant MXene through low-temperature molten salt system |
| CN115504474A (en) * | 2022-11-03 | 2022-12-23 | 滁州学院 | Preparation of oxygen-doped O-Ti 3 C 2 T x Method for two-dimensional material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114956085A (en) * | 2021-02-26 | 2022-08-30 | 苏州北科纳米科技有限公司 | Method for preparing antioxidant MXene through low-temperature molten salt system |
| CN115504474A (en) * | 2022-11-03 | 2022-12-23 | 滁州学院 | Preparation of oxygen-doped O-Ti 3 C 2 T x Method for two-dimensional material |
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