CN112354372B - Modified titanium carbide layered film and preparation method thereof - Google Patents

Modified titanium carbide layered film and preparation method thereof Download PDF

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CN112354372B
CN112354372B CN202011204486.2A CN202011204486A CN112354372B CN 112354372 B CN112354372 B CN 112354372B CN 202011204486 A CN202011204486 A CN 202011204486A CN 112354372 B CN112354372 B CN 112354372B
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titanium carbide
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aluminum
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CN112354372A (en
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王磊
朱甲妮
王琎
贺苗露
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Xian University of Architecture and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/50—Control of the membrane preparation process

Abstract

The invention discloses a modified titanium carbide layered film and a preparation method thereof, wherein the method comprises the following steps: step 1, preparing and obtaining two-dimensional titanium carbideA nanosheet solution; preparing to obtain a hydroxyl aluminum solution; step 2, mixing and stirring the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution to obtain Al 13 ‑Ti 3 C 2 T x A nanosheet solution; step 3, based on Al obtained in step 2 13 ‑Ti 3 C 2 T x Making Al from nanosheet solution by vacuum filtration 13 ‑Ti 3 C 2 T x And depositing the nanosheet on the acetate fiber membrane or the PVDF membrane, and drying in vacuum at room temperature to obtain the modified titanium carbide layered membrane. In the invention, aluminum hydroxide is introduced into the preparation process of the membrane, so that the swelling phenomenon of the two-dimensional membrane can be effectively inhibited, and the spacing between the titanium carbide two-dimensional membrane layers can be regulated and controlled within a certain range by simply adjusting the preparation conditions of the aluminum hydroxide.

Description

Modified titanium carbide layered film and preparation method thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a modified titanium carbide layered membrane and a preparation method thereof.
Background
The membrane separation technology is known as 'the green separation technology of the 21 st century', and provides a reliable, efficient and clean method for selective transmission of water and ions. The thickness of the emerging two-dimensional membrane can be as low as atomic level, and the transmission resistance of the membrane can be reduced to the greatest extent, so that high-flux separation is realized. The titanium carbide two-dimensional film is a two-dimensional film which is formed by stacking titanium carbide nano sheets and has an ordered layered structure, has abundant nano-scale channels and can be used for substance transfer, and the interlayer distance of the titanium carbide two-dimensional film can be adjusted by modification.
Up to now, there have been a lot of studies on the application of two-dimensional membranes for various fields such as ion sieving, gas separation, and organic solvent separation. The interlayer spacing of the two-dimensional membrane plays a key role in determining separation performance, but the two-dimensional membrane generates a swelling phenomenon in an aqueous solution so that the interlayer spacing cannot be stabilized at a single size, thereby causing the reduction of the separation performance in the separation process. Aiming at the problem of unstable spacing of two-dimensional films, a great deal of research is carried out by scholars, wherein Lu and the like adopt a self-crosslinking reaction method to stabilize the spacing of the two-dimensional films of titanium carbide
Figure BDA0002756598490000011
Nair et al control interlayer spacing using a method of physically confining the wrapping to the graphene film by a resin. However, the above method has the disadvantages of complicated preparation process, etc.
In summary, a new modified titanium carbide two-dimensional layered film and a preparation method thereof are needed.
Disclosure of Invention
The invention aims to provide a modified titanium carbide layered film and a preparation method thereof, so as to solve one or more technical problems. In the invention, aluminum hydroxide is introduced into the preparation process of the membrane, so that the swelling phenomenon of the two-dimensional membrane can be effectively inhibited, and the spacing between the titanium carbide two-dimensional membrane layers can be regulated and controlled within a certain range by simply adjusting the preparation conditions of the aluminum hydroxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a modified titanium carbide layered film, which comprises the following steps:
step 1, preparing a two-dimensional titanium carbide nanosheet solution; preparing to obtain a hydroxyl aluminum solution;
step 2, mixing and stirring the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution to obtain Al 13 -Ti 3 C 2 T x A nanosheet solution;
step 3, based on Al obtained in step 2 13 -Ti 3 C 2 T x Making Al from nanosheet solution by vacuum filtration 13 -Ti 3 C 2 T x And (3) depositing the nanosheets on an acetate fiber membrane or a PVDF membrane, and drying at room temperature in vacuum to obtain the modified titanium carbide layered membrane.
The further improvement of the invention is that, in step 1, the step of preparing the two-dimensional titanium carbide nanosheet solution specifically comprises: adding titanium aluminum carbide into a prepared etchant solution, and stirring for reaction for a preset time to obtain a solid precipitate as a reaction product; cleaning the reaction product until the pH value of the upper solution is more than or equal to 5; and centrifuging and diluting the upper layer solution to obtain a two-dimensional titanium carbide nanosheet solution.
The further improvement of the invention is that in the step 1, the etching agent solution prepared in advance is the etching agent solution prepared by dissolving lithium fluoride in hydrochloric acid; wherein, the molar ratio of the lithium fluoride to the hydrochloric acid is 0.2-0.4, and the mass ratio of the lithium fluoride to the titanium aluminum carbide is 1.0-1.2; the stirring reaction preset time specifically comprises the following steps: reacting for 20-48 hours at 40-60 ℃; the concentration of the titanium carbide nano-sheet in the obtained two-dimensional titanium carbide nano-sheet solution is 0.1-0.2 mg/mL.
The further improvement of the invention is that in the step 1, the step of preparing the aluminum hydroxide solution specifically comprises the following steps: will contain OH - Is added dropwise to the solution containing Al 3+ To obtain a mixed solution; wherein, OH in the mixed solution - With Al 3+ The molar ratio of (A) to (B) is 2.0 to 2.4.
The invention is further improved in that, in step 1, the catalyst contains OH - The solution of (2) is NaOH solution or KOH solution; containing Al 3 + The solution of (A) is AlCl 3 Solution, al 2 (SO 4 ) 3 And (3) solution.
The invention is further improved in that in the step 2, the mixing and stirring time ranges from 8 to 12 hours.
In step 2, the preparation method of the aged aluminum hydroxide solution comprises the following steps: and (2) stirring the hydroxyl aluminum solution obtained in the step (1) at the temperature of between 60 and 80 ℃ for 2 to 4 hours, and aging the solution at room temperature for 7 to 15 days.
The invention has the further improvement that in the step 2, when the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution are mixed and stirred, the mass ratio of the hydroxyl aluminum to the titanium carbide is (360-90): 1.
the interval between the modified titanium carbide layered films is
Figure BDA0002756598490000031
Within the range.
The invention relates to a modified titanium carbide layered film, which is prepared by the following stepsAt a distance of
Figure BDA0002756598490000032
Within the range.
Compared with the prior art, the invention has the following beneficial effects:
the modification method provided by the invention is simple in process and low in cost, and the hydroxyl aluminum is introduced into the membrane preparation process, so that the swelling phenomenon of the two-dimensional membrane can be effectively inhibited, and the spacing between the titanium carbide two-dimensional membrane layers can be regulated and controlled within a certain range by simply adjusting the preparation conditions of the hydroxyl aluminum. The preparation method of the modified titanium carbide layered two-dimensional film provided by the invention has the advantages that the separation films with different layer intervals are provided, the layer intervals of the layered film are fixed, and the problem of common swelling of the two-dimensional layered film in an aqueous solution is solved; the preparation method of the modified titanium carbide layered two-dimensional film provided by the invention has the advantages of simple preparation process, low cost and controllable interlayer spacing.
In the method of the present invention, OH in the mixed solution - With Al 3+ The molar ratio of (A) to (B) is 2.0 to 2.4 when OH is contained - With Al 3+ When the molar ratio of (B) is more than 2.5, aluminum hydroxide precipitation is generated; the concentration of the titanium carbide nanosheet in the two-dimensional titanium carbide nanosheet solution is 0.1-0.2 mg/mL, and the uniform titanium carbide layered membrane can be obtained by using the concentration to perform vacuum filtration.
The invention can lead the spacing of the titanium carbide two-dimensional film layers to be within the range of the preparation condition of the hydroxyl aluminum by simply adjusting the preparation condition of the hydroxyl aluminum
Figure BDA0002756598490000033
And regulating and controlling within the range.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below; it is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram illustrating a method for preparing a modified titanium carbide two-dimensional layered film according to an embodiment of the present invention;
FIG. 2 is a schematic diagram showing the comparison of the distances between the titanium carbide layered films before and after modification with aluminum hydroxide in the embodiment of the present invention; wherein, fig. 2 (a) is a schematic diagram of the change of the layer spacing of an undisturbed titanium carbide layered film in different ionic solutions, and fig. 2 (b) is a schematic diagram of the stable layer spacing of an aluminum hydroxyl modified titanium carbide layered film in different ionic solutions;
FIG. 3 is a schematic diagram showing the influence of the titanium carbide layered film before and after modification of aluminum hydroxide on the sodium ion and aluminum ion sieving performance in the example of the present invention.
Detailed Description
In order to make the purpose, technical effect and technical solution of the embodiments of the present invention clearer, the following clearly and completely describes the technical solution of the embodiments of the present invention with reference to the drawings in the embodiments of the present invention; it is to be understood that the described embodiments are part of the present invention. Other embodiments, which can be derived by one of ordinary skill in the art from the disclosed embodiments without inventive faculty, are intended to be within the scope of the invention.
Referring to fig. 1, a method for preparing a modified titanium carbide layered film according to an embodiment of the present invention includes the following steps:
step 1, preparing a titanium carbide nanosheet solution, comprising: adding titanium aluminum carbide into a prepared etchant solution, stirring and reacting for a preset time, and taking a solid precipitate as a reaction product; cleaning the reaction product until the pH value of the upper solution is more than or equal to 5; centrifuging and diluting the upper layer solution to obtain a two-dimensional titanium carbide nanosheet solution;
step 2, preparing a hydroxyl aluminum solution, which comprises the following steps: will contain OH - Is added dropwise to the solution containing Al 3+ To obtain a mixed solution; in the mixed solution, OH - With Al 3+ The molar ratio of (A) to (B) is 2.0 to 2.4;
step 3, mixing the titanium carbide solution and the aged hydroxyl aluminum solution, and stirring (8-12 hours)) Obtaining Al 13 -Ti 3 C 2 T x A nanosheet solution; al is filtered by vacuum filtration 13 -Ti 3 C 2 And depositing the Tx nanosheet on the acetate fiber membrane or the PVDF membrane, and drying in vacuum at room temperature to obtain the modified titanium carbide layered film.
In the embodiment of the invention, the pre-prepared etchant solution is obtained by dissolving lithium fluoride in hydrochloric acid; wherein, the proportion relation of the lithium fluoride and the hydrochloric acid is that the molar ratio of the lithium fluoride to the hydrochloric acid is 0.2-0.4. The preset time of the stirring reaction is specifically 20 to 48 hours at the temperature of between 40 and 60 ℃. The concentration of the titanium carbide nanosheet in the two-dimensional titanium carbide nanosheet solution obtained in the step 1 is 0.1-0.2 mg/mL.
In the embodiment of the present invention, the aging of the aluminum hydroxide solution specifically includes stirring the mixed solution obtained in step 2 at 80 ℃ for 2 hours, and aging at room temperature for 7 to 15 days before use.
In the embodiment of the invention, the interlayer spacing of the modified titanium carbide layered film can be effectively regulated and controlled by adjusting the aging time and the doping amount of the hydroxyl aluminum solution, and the specific parameters are shown in the following table:
Figure BDA0002756598490000051
the modified titanium carbide film prepared by the method has adjustable interlayer spacing, and titanium carbide films with different interlayer spacing have the characteristic of swelling resistance, so that the problem of swelling of a two-dimensional layered film in an aqueous solution is solved, and the preparation process is simple and low in cost.
Step 1 of the embodiment of the present invention specifically includes: 1g of lithium fluoride was dissolved in 20mL of 6-12M hydrochloric acid to obtain an etchant solution, and 1g of Ti was added 3 AlC 2 Stirring the mixture at 45 ℃ for reaction for 24 hours, repeatedly washing the mixture by deionized water after the reaction is finished until the pH value of the solution is more than 5, and finally centrifuging the solution at 4000rpm for 1 hour to obtain stable two-dimensional Ti 3 C 2 T x And (3) measuring the concentration of the nanosheet solution by using a spectrophotometer, and preparing 0.2mg/mL titanium carbide solution for later use.
Step 2 of the embodiment of the present invention specifically includes: preparation of aluminum hydroxide solution: 480mL of 0.3M NaOH was added dropwise to 150mL of 0.4M AlCl at a rate of 1mL/min in an 80 ℃ water bath 3 To the final [ OH ] - ]/[Al 3+ ]Up to 2.4. Then, the mixed solution was further stirred at 80 ℃ for 2 hours and aged at room temperature for 7 to 15 days before use.
Step 3 of the embodiment of the present invention specifically includes: taking 250mL of the titanium carbide solution with the concentration of 0.2mg/mL and a certain volume of aluminum hydroxide to the constant volume of 500mL, mixing and stirring for 12h, and performing vacuum filtration to enable Al to be in a form of vacuum filtration 13 -Ti 3 C 2 T x Regularly depositing nano sheets on an acetate fiber membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain modified Ti 3 C 2 T x A film.
The method of the embodiment of the invention has the following beneficial effects: ti 3 C 2 T x The undisturbed lamellar membrane formed by stacking the nanosheets in parallel can generate structural deformation due to the insertion of water molecules and ions in an aqueous solution environment. And Al in the aluminum hydroxide solution 13 Polycation and Ti 3 C 2 T x Oppositely charged nature of the nanosheets, al 13 The ions will be evenly distributed in the Ti during the mixing process 3 C 2 T x The nanosheets are on the surface and are uniformly distributed between the layered membranes during vacuum filtration. Al (aluminum) 13 And strong electrostatic force between adjacent nanosheets effectively suppresses Ti 3 C 2 T x Swelling phenomenon of the membrane. Adjusting Al with different proportions and aging time of 7 days 13 Polycations by strengthening or weakening Al 13 With Ti 3 C 2 T x The acting force between the nano sheets controls the reduction or the increase of the space between the two-dimensional film layers; adjusting Al with different aging times 13 The polycation is due to Al in the aluminum hydroxide solution with the aging time 13 The ion volume is increased continuously, so that the hydroxyl aluminum solution with the aging time of 15 days can expand and fix the two-dimensional film interval
Figure BDA0002756598490000061
Example 1
(1) Preparation of a film comprising: 1g of lithium fluoride was dissolved in 20mL of 9M hydrochloric acid to obtain an etchant solution, and then 1g of Ti was added 3 C 2 T x Stirring the mixture at 45 ℃ for reaction for 24 hours, repeatedly washing the mixture by deionized water after the reaction is finished until the pH value of the solution is more than 5, and finally centrifuging the solution at 4000rpm for 1 hour to obtain stable two-dimensional Ti 3 C 2 T x A nanosheet solution. The concentration of Ti was measured by a spectrophotometer to prepare 0.1mg/mL of Ti 3 C 2 T x 500mL of nanosheet solution, and vacuum filtration is adopted to obtain Ti 3 C 2 T x Regularly depositing nano sheets on an acetate fiber membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain undisturbed Ti 3 C 2 T x Film of, in the dry state, a layer spacing of
Figure BDA0002756598490000063
In aqueous solutions of different cations the layers are spaced apart
Figure BDA0002756598490000062
To change between.
In the above two dimensions of Ti 3 C 2 T x Based on the nanosheet solution, 0.2mg/mL of Ti is taken 3 C 2 T x Mixing and stirring 250mL of nanosheet solution and 250mL of hydroxy aluminum solution with aging time of 7 days for 12h, and performing vacuum filtration to obtain Al 13 -Ti 3 C 2 T x Regularly depositing nano sheets on an acetate fiber membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain modified Ti 3 C 2 T x Film of the interlayer spacing
Figure BDA0002756598490000064
Taking 0.2mg/mL Ti 3 C 2 T x Adding 250mL of nanosheet solution and 125mL of hydroxy aluminum solution with aging time of 7 days to a constant volume of 500mL, mixing and stirring for 12h, and performing vacuum filtration to obtain Al 13 -Ti 3 C 2 T x Regularly depositing nano sheets on an acetate fiber membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain modified Ti 3 C 2 T x Film of interlayer spacing of
Figure BDA0002756598490000065
Taking 0.2mg/mL Ti 3 C 2 T x Adding 250mL of nanosheet solution and 50mL of hydroxy aluminum solution with the aging time of 7 days into 500mL of constant volume, mixing and stirring for 12h, and performing vacuum filtration to enable Al to be in a pure water state 13 -Ti 3 C 2 T x Regularly depositing nano sheets on an acetate fiber membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain modified Ti 3 C 2 T x Film of interlayer spacing of
Figure BDA0002756598490000071
Taking 0.2mg/mL Ti 3 C 2 T x Adding 250mL of nanosheet solution and 50mL of hydroxy aluminum solution with aging time of 15 days to a constant volume of 500mL, mixing and stirring for 12h, and performing vacuum filtration to obtain Al 13 -Ti 3 C 2 T x Regularly depositing nano sheets on an acetate fiber membrane with the aperture of 0.22 mu m, and drying at room temperature to obtain modified Ti 3 C 2 T x Film of the interlayer spacing
Figure BDA0002756598490000072
(2) And (3) verifying the swelling resistance of the film: the change of the interlayer spacing of the modified titanium carbide layered film in different solutions was examined by X-ray diffraction (XRD) analysis, and the titanium carbide thin film as it is and the modified Ti film prepared using the titanium carbide layered film of example 1 were used 3 C 2 T x Film, it can be seen from FIG. 2 that the distance between the undisturbed film layers is changed to different degrees in different solutions than the original Ti in DI water 3 C 2 T x The interlayer spacing is increased in the solution of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride and aluminum chloride, compared with that in the solution of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride and aluminum chlorideThe distance between rubidium chloride and tin chloride layers is reduced; the aluminum hydroxide modified titanium carbide film not only has adjustable interlayer spacing, but also can inhibit swelling phenomenon in different ionic water solutions.
(3) Spacing the layers at a distance of
Figure BDA0002756598490000073
The modified titanium carbide layered membrane is placed in a U-shaped filtering device, the permeation side of the modified membrane is pure water, the stock solution side is a 0.5M mixed solution of sodium chloride and aluminum chloride, a point-shaped graph of ion permeation concentration changing along with time is drawn by monitoring the change of two ion concentrations in the pure water on the permeation side along with time, the slope of a fitted straight line represents the ion permeation speed, as shown in figure 3, na in an original membrane + /Al 3+ Has an ion permeation rate of about 7.3, and has Na content in the aluminum hydroxide-modified titanium carbide layered film + /Al 3+ The ion permeation rate was about 173, which was significantly increased. Therefore, the modified titanium carbide layered film can better realize Na + 、Al 3+ Separation of (3).
Example 2
The preparation method of the modified titanium carbide layered film is characterized by comprising the following steps of:
step 1, preparing a two-dimensional titanium carbide nanosheet solution; preparing and obtaining a hydroxyl aluminum solution;
step 2, mixing and stirring the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution to obtain Al 13 -Ti 3 C 2 T x A nanosheet solution;
step 3, based on Al obtained in step 2 13 -Ti 3 C 2 T x Making Al of nanosheet solution by vacuum filtration 13 -Ti 3 C 2 T x And (3) depositing the nanosheets on an acetate fiber membrane or a PVDF membrane, and drying at room temperature in vacuum to obtain the modified titanium carbide layered membrane.
In step 1, the step of preparing the two-dimensional titanium carbide nanosheet solution specifically comprises: adding titanium aluminum carbide into the prepared etchant solution, stirring and reacting for a preset time to obtainObtaining solid precipitate as a reaction product; cleaning the reaction product until the pH value of the upper layer solution is more than or equal to 5; and centrifuging and diluting the upper layer solution to obtain a two-dimensional titanium carbide nanosheet solution. The pre-prepared etchant solution is prepared by dissolving lithium fluoride in hydrochloric acid; wherein the molar ratio of the lithium fluoride to the hydrochloric acid is 0.2; the preset stirring reaction time specifically comprises the following steps: reacting for about 48 hours at 40 ℃; the concentration of the titanium carbide nanosheet in the obtained two-dimensional titanium carbide nanosheet solution is 0.1mg/mL. The step of preparing the hydroxyl aluminum solution specifically comprises the following steps: will contain OH - Is added dropwise to the solution containing Al 3+ To obtain a mixed solution; wherein, OH in the mixed solution - With Al 3+ Is 2.0. Containing OH - The solution of (A) is NaOH solution; containing Al 3+ The solution of (A) is AlCl 3 And (3) solution. In the step 2, the time range of mixing and stirring is 8-12 hours. In step 2, the preparation method of the aged aluminum hydroxide solution comprises the following steps: and (3) stirring the hydroxyl aluminum solution obtained in the step (1) at 60 ℃ for 4 hours, and aging at room temperature for 7-15 days.
Example 3
The preparation method of the modified titanium carbide layered film is characterized by comprising the following steps of:
step 1, preparing a two-dimensional titanium carbide nanosheet solution; preparing and obtaining a hydroxyl aluminum solution;
step 2, mixing and stirring the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution to obtain Al 13 -Ti 3 C 2 T x A nanosheet solution;
step 3, based on Al obtained in step 2 13 -Ti 3 C 2 T x Making Al of nanosheet solution by vacuum filtration 13 -Ti 3 C 2 T x And (3) depositing the nanosheets on an acetate fiber membrane or a PVDF membrane, and drying at room temperature in vacuum to obtain the modified titanium carbide layered membrane.
In step 1, the step of preparing the two-dimensional titanium carbide nanosheet solution specifically comprises: aluminizing the carbonAdding titanium into a prepared etchant solution, and stirring for reaction for a preset time to obtain a solid precipitate as a reaction product; cleaning the reaction product until the pH value of the upper layer solution is more than or equal to 5; and centrifuging and diluting the upper layer solution to obtain a two-dimensional titanium carbide nanosheet solution. The pre-prepared etchant solution is prepared by dissolving lithium fluoride in hydrochloric acid; wherein the molar ratio of the lithium fluoride to the hydrochloric acid is 0.4; the stirring reaction preset time specifically comprises the following steps: reacting for 20 hours at the temperature of 60 ℃; the concentration of the titanium carbide nanosheet in the obtained two-dimensional titanium carbide nanosheet solution is 0.2mg/mL. The step of preparing the hydroxyl aluminum solution specifically comprises the following steps: will contain OH - Is added dropwise to the solution containing Al 3+ To obtain a mixed solution; wherein, OH in the mixed solution - With Al 3+ Is 2.4. Containing OH - The solution of (2) is a KOH solution; containing Al 3+ The solution of (A) is Al 2 (SO 4 ) 3 And (3) solution. In the step 2, the mixing and stirring time ranges from 8 to 12 hours. In step 2, the preparation method of the aged aluminum hydroxide solution comprises the following steps: and (3) stirring the hydroxyl aluminum solution obtained in the step (1) at the temperature of 80 ℃ for 2 hours, and aging at room temperature for 7-15 days.
Example 4
The preparation method of the modified titanium carbide layered film is characterized by comprising the following steps of:
step 1, preparing a two-dimensional titanium carbide nanosheet solution; preparing and obtaining a hydroxyl aluminum solution;
step 2, mixing and stirring the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution to obtain Al 13 -Ti 3 C 2 T x A nanosheet solution;
step 3, based on Al obtained in step 2 13 -Ti 3 C 2 T x Making Al of nanosheet solution by vacuum filtration 13 -Ti 3 C 2 T x And depositing the nanosheet on the acetate fiber membrane or the PVDF membrane, and drying in vacuum at room temperature to obtain the modified titanium carbide layered membrane.
Wherein the steps1, the step of preparing the two-dimensional titanium carbide nanosheet solution specifically comprises: adding titanium aluminum carbide into a prepared etchant solution, and stirring for reaction for a preset time to obtain a solid precipitate as a reaction product; cleaning the reaction product until the pH value of the upper solution is more than or equal to 5; and centrifuging and diluting the upper layer solution to obtain a two-dimensional titanium carbide nanosheet solution. The pre-prepared etchant solution is prepared by dissolving lithium fluoride in hydrochloric acid; wherein the molar ratio of the lithium fluoride to the hydrochloric acid is 0.3; the preset stirring reaction time specifically comprises the following steps: reacting for 24 hours at the temperature of 45 ℃; the concentration of the titanium carbide nanosheet in the obtained two-dimensional titanium carbide nanosheet solution is 0.15mg/mL. The step of preparing the hydroxyl aluminum solution specifically comprises the following steps: will contain OH - Is added dropwise to the solution containing Al 3+ To obtain a mixed solution; wherein, OH in the mixed solution - With Al 3+ Is 2.2. Containing OH - The solution of (A) is NaOH solution containing Al 3+ The solution of (A) is Al 2 (SO 4 ) 3 And (3) solution. In the step 2, the mixing and stirring time ranges from 8 to 12 hours. In step 2, the preparation method of the aged aluminum hydroxide solution comprises the following steps: and (3) stirring the hydroxyl aluminum solution obtained in the step (1) at 70 ℃ for 3 hours, and aging at room temperature for 7-15 days.
Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can make modifications and equivalents to the embodiments of the present invention without departing from the spirit and scope of the present invention, which is set forth in the claims of the present application.

Claims (4)

1. The preparation method of the modified titanium carbide layered film is characterized by comprising the following steps of:
step 1, preparing a two-dimensional titanium carbide nanosheet solution; preparing and obtaining a hydroxyl aluminum solution;
step 2, taking a two-dimensional titanium carbide nanosheet solution and agingMixing and stirring the hydroxylated aluminum solution to obtain Al 13 -Ti 3 C 2 T x A nanosheet solution;
step 3, based on Al obtained in step 2 13 -Ti 3 C 2 T x Making Al of nanosheet solution by vacuum filtration 13 -Ti 3 C 2 T x The nano sheet is deposited on an acetate fiber film or a PVDF film, and is dried in vacuum at room temperature to obtain a modified titanium carbide layered film;
in step 1, the step of preparing the two-dimensional titanium carbide nanosheet solution specifically comprises: adding titanium aluminum carbide into a prepared etchant solution, and stirring for reaction for a preset time to obtain a solid precipitate as a reaction product; cleaning the reaction product until the pH value of the upper layer solution is more than or equal to 5; centrifuging and diluting the upper layer solution to obtain a two-dimensional titanium carbide nanosheet solution; in the step 1, the pre-prepared etchant solution is prepared by dissolving lithium fluoride in hydrochloric acid; wherein the molar ratio of the lithium fluoride to the hydrochloric acid is 0.2-0.4; the mass ratio of the lithium fluoride to the titanium aluminum carbide is 1.0-1.2; the preset stirring reaction time specifically comprises the following steps: reacting for 20-48 hours at 40-60 ℃; the concentration of the titanium carbide nano sheet in the obtained two-dimensional titanium carbide nano sheet solution is 0.1-0.2 mg/mL; in step 1, the step of preparing the aluminum hydroxide solution specifically comprises: will contain OH - Is added dropwise to the solution containing Al 3+ To obtain a mixed solution; wherein, OH in the mixed solution - With Al 3+ The molar ratio of (A) to (B) is 2.0-2.4;
in the step 2, the mixing and stirring time range is 8-12 hours; in step 2, the preparation method of the aged aluminum hydroxide solution comprises the following steps: stirring the hydroxyl aluminum solution obtained in the step 1 at the temperature of between 60 and 80 ℃ for 2 to 4 hours, and aging the solution at room temperature for 7 to 15 days; in the step 2, when the two-dimensional titanium carbide nanosheet solution and the aged hydroxyl aluminum solution are mixed and stirred, the mass ratio of the hydroxyl aluminum to the titanium carbide is (360-90): 1;
the preparation method of the modified titanium carbide layered film regulates and controls the spacing between the titanium carbide two-dimensional film layers within a certain range by adjusting the aging time of aluminum hydroxide and the proportion of aluminum hydroxide and the two-dimensional titanium carbide nanosheets.
2. The method for preparing a modified titanium carbide layered film according to claim 1, wherein in step 1, OH is contained - The solution of (2) is NaOH solution or KOH solution; containing Al 3+ The solution of (A) is AlCl 3 Solution, al 2 （SO 4 ） 3 And (3) solution.
3. A modified titanium carbide layered film produced by the method of producing a modified titanium carbide layered film of claim 1 or 2, wherein the modified titanium carbide layered film has a spacing in the range of from 11.5 to 20.0 a.
4. A modified titanium carbide layered film prepared by the method of preparing a modified titanium carbide layered film of claim 1 or 2, wherein the modified titanium carbide layered film has a spacing in the range of 11.5 to 14.0 a.
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