CN116173745A - Preparation method of high-performance MXene@PEI/IL film - Google Patents

Preparation method of high-performance MXene@PEI/IL film Download PDF

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CN116173745A
CN116173745A CN202310114511.5A CN202310114511A CN116173745A CN 116173745 A CN116173745 A CN 116173745A CN 202310114511 A CN202310114511 A CN 202310114511A CN 116173745 A CN116173745 A CN 116173745A
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pei
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骆文佳
李瓛
牛振华
李健
张析
王进龙
周涛
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Northwest Research Institute of Mining and Metallurgy
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Abstract

The invention relates to a preparation method of a high-performance MXene@PEI/IL film, which comprises the following steps: preparation of two-dimensional layered Ti by in-situ etching 3 C 2 T x mXene nanoplatelets: liF and HCl were added to a magnetically stirred PTFE beakerIn (a) and (b); slowly adding MAX powder into a PTFE beaker containing the mixed solution, stirring at a constant temperature of 45 ℃ for 24 hours, and centrifuging to obtain a precipitate; the precipitate was washed several times up to pH>7, the time is up to 7; finally, the obtained precipitate is subjected to ultrasonic stripping and centrifugation to obtain single-layer two-dimensional Ti 3 C 2 T x An MXene nanoplatelet solution; secondly, mixing the MXene nanosheet solution and the PEI solution, and magnetically stirring in an argon protection environment to obtain a mixed solution; filtering the mixed solution on a polytetrafluoroethylene filter membrane through a vacuum filter device, and drying at room temperature to obtain an MXene@PEI membrane; and fourthly, spin-coating the ionic liquid IL with different concentrations on the upper surface of the MXene@PEI film, and drying to obtain a series of MXene@PEI/IL films. The preparation process is simple, and the obtained MXene@PEI/IL film has high gas permeability, excellent thermal stability and durability.

Description

Preparation method of high-performance MXene@PEI/IL film
Technical Field
The invention relates to the technical field of composite materials and the technical field of coatings, in particular to a preparation method of a high-performance MXene@PEI/IL film.
Background
With the rapid development of economy and the increasing demand for energy, carbon dioxide (CO) in the atmosphere 2 ) Has become one of the major problems of global concern due to the significant increase in concentration. Natural gas will be a major source of energy worldwide, both now and in the future. However, CO in natural gas 2 Can corrode natural gas pipelines, reduce combustion values, increase compression cost, and the like. Therefore, there is an urgent need to develop an effective method for reducing CO in fuel gas and natural gas 2 Is a concentration of (3).
In conventional CO 2 In the separation method, the amino solvent is mature CO 2 Capture technology, however, has significant drawbacks such as high energy costs and potential environmental risks. Compared with the traditional method for absorbing and separating the amino solvent, the membrane separation has the characteristics of low cost, no phase change and environmental friendliness, and is widely applied to CO in gas mixtures 2 Is used for the large-scale treatment of natural gas and flue gasCO in (b) 2 Has wide application prospect.
MXene, also known as "graphene-like oxide," is a class of metal carbides and metal nitrides having a two-dimensional layered structure. The rich functional groups on the surface of the MXene endow the MXene with high surface area, biocompatibility, hydrophilicity, low diffusion resistance, activated metal hydroxide sites and excellent conductivity. The MXene material layer has a fluidized structure and rich functional groups on the surface, so that the MXene material layer becomes a new star in the field of two-dimensional nano materials. The layered structure of MXene imparts a special mass transport channel to the two-dimensional MXene film, which allows gas molecules and other small molecules to move rapidly in the layered structure.
In addition, ionic Liquids (IL) are salts consisting of organic cations and inorganic or organic anions, which are liquid at room temperature. IL has the excellent performances of low volatility, good thermal stability, adjustable physical and chemical properties and the like, and is a potential gas separation material. IL has a high CO content 2 Solubility and almost no vapor pressure, and can remarkably improve CO 2 Because of the strong interfacial affinity of IL and the prevention of the formation of non-selective voids in the membrane. Thus, by combining MXene with IL in a manner that provides nanochannels and has a CO-philic effect with two-dimensional MXene nanoplatelets 2 The IL formed by the method has more excellent performance, and is beneficial to eliminating CO in natural gas and flue gas 2 。
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance MXene@PEI/IL film, which is simple in preparation process and easy to realize.
In order to solve the problems, the preparation method of the high-performance MXene@PEI/IL film comprises the following steps:
preparation of two-dimensional layered Ti by in-situ etching 3 C 2 T x mXene nanoplatelets:
LiF and HCl at 8M were mixed at 1: 11-12.5 mass to volume ratio is added into a magnetically stirred PTFE beaker; the MAX powder was then slowly added to the PTFE beaker containing the above mixed solution at 45Stirring at constant temperature for 24 hours, and centrifuging to obtain a precipitate; the precipitate was washed several times up to pH>7, the time is up to 7; finally, the obtained precipitate is subjected to ultrasonic stripping and centrifugation to obtain single-layer two-dimensional Ti 3 C 2 T x An MXene nanoplatelet solution; the mass ratio of the MAX powder to the LiF is 1:1.8;
mixing an MXene nanosheet solution with the concentration of 1mg/mL and a PEI solution with the mass fraction of 3.5wt%, and magnetically stirring for 30min in an argon protection environment to obtain a mixed solution;
filtering the mixed solution on a Polytetrafluoroethylene (PTFE) filter membrane through a vacuum filter device, and drying for 2-8 hours at room temperature to obtain an MXene@PEI membrane;
and fourthly, spin-coating ionic liquid IL with different concentrations on the upper surface of the MXene@PEI film by using a spin-coating machine, drying for 8 hours at room temperature, and then drying for 24 hours in a vacuum oven at 45 ℃ to obtain a series of MXene@PEI/IL films.
In the step (II), the MXene nano-sheet solution with the concentration of 1mg/mL is prepared by mixing MXene nano-sheets with deionized water according to a ratio of 1:3, and uniformly mixing the obtained solution.
The PEI solution with the mass fraction of 3.5wt% in the step (II) is prepared by mixing PEI and deionized water according to a weight ratio of 1:7 mass ratio of the mixture to the solution obtained by uniform mixing.
In the step (II), the mass ratio of the MXene nano-sheet solution to the PEI solution is 3: 2-7.
And in the step III, the thickness of the PTFE filter membrane is 50mm, and the pore diameter is 0.22um.
In the step, the mass ratio of the MXene@PEI film to the ionic liquid IL is 1: 1.2-1: 2.1.
in the step, the ionic liquid IL refers to 1-vinyl-3-ethylimidazole tetrafluoroborate.
Compared with the prior art, the invention has the following advantages:
1. the method comprises the steps of firstly modifying the surface of MXene by PEI, improving the compatibility of the MXene, then carrying out suction filtration on a MXene@PEI solution on a PTFE filter membrane by a vacuum suction filtration device, finally carrying out spin coating on the upper surface of the MXene@PEI membrane by IL with different concentrations by a spin coater, and drying to obtain the high-performance MXene@PEI/IL membrane.
FIG. 1a shows a single layer MXene nanoplatelet extraction filter, and it can be seen that there are many folds on the surface. This is due to the rapid assembly of the MXene nanoplatelets and the relatively rough surface of the PTFE substrate. The MXene nanoplatelets can also be observed to have a layered structure on a cross-sectional scanning electron microscope of the MXene film. In addition, the upper surface of the mxene@pei film was relatively smooth (fig. 1 b), probably due to the filling of the low-lying areas of the MXene wrinkles with PEI, and the film thickness remained essentially unchanged. After spin-coating of different concentrations of IL, the pitch of the MXene nanoplatelets increased significantly with increasing spin-coating IL concentration, the upper surface of the film became smooth and dense, but a lamellar structure of MXene could still be observed (fig. 1c, d, e, f shows spin-coating IL concentrations of 20wt%,25wt%,30wt% and 35wt%, respectively). The layered structure provides selective passage of gas molecules during separation and, in addition, due to IL versus CO 2 The affinity and the diffusion effect of nano-flow channels provided by MXene nano-sheets with layered structures realize the CO 2 High permeability to CO 2 /N 2 And CO 2 /CH 4 Is a high selectivity of (2). As can be seen from the EDS diagram corresponding to the cross-section of fig. 1d, the elements Ti, F, N, O are uniformly distributed in the selected layer. This demonstrates that the MXene nanoplatelets have good compatibility with PEI and IL.
2. Compared with other reported gas separation membranes, the MXene@PEI/IL membrane has high gas permeability, excellent thermal stability and durability, and can be widely applied to separating CO in natural gas and flue gas 2 And (3) gas.
3. The preparation process is simple and easy to realize.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is an SEM and EDS image of the upper surface and cross section of a single layer of MXene nanoplatelet filter and a MXene@PEI/IL membrane prepared according to the invention.
FIG. 2 is a graph of MXene@PEI/IL membrane pairs with varying IL loadings in accordance with the invention 2 /N 2 And CO 2 /CH 4 Is a test of the separation performance of the above-mentioned material.
FIG. 3 is a graph showing the mixture of gases CO at various temperatures for a MXene@PEI/IL film of the invention with an IL loading of 25wt% 2 /N 2 And CO 2 /CH 4 Is a test of the separation performance of the above-mentioned material.
FIG. 4 is a graph of the mixed gas CO under continuous testing for a MXene@PEI/IL film of the invention with an IL loading of 25wt% 2 /N 2 And CO 2 /CH 4 Is a test of the separation performance of the above-mentioned material.
FIG. 5 is a comparison of separation performance of an MXene@PEI/IL membrane of the invention with an IL loading of 25 wt.% compared to other reported gas separation membranes.
Detailed Description
A preparation method of a high-performance MXene@PEI/IL film comprises the following steps:
preparation of two-dimensional layered Ti by in-situ etching 3 C 2 T x mXene nanoplatelets:
LiF and HCl at 8M were mixed at 1: 11-12.5 mass to volume ratio (g/ml) is added into a magnetically stirred PTFE beaker; the MAX powder was then slowly added to the PTFE beaker containing the above mixed solution, with a mass ratio of MAX powder to LiF (g/g) of 1:1.8. stirring at 45deg.C for 24 hr, and centrifuging to obtain precipitate; the precipitate was washed several times with 1M HCl and then with deionized water until pH>7, the time is up to 7; finally, the obtained precipitate is subjected to ultrasonic stripping and centrifugation to obtain single-layer two-dimensional Ti 3 C 2 T x MXene nanoplatelet solutions.
The preparation method comprises the following steps of (1) mixing an MXene nanosheet solution with the concentration of 1mg/mL and a PEI solution with the mass fraction of 3.5 and wt percent according to the following weight percentage: mixing the materials according to the mass ratio (g/g) of 2-7, and magnetically stirring the mixture for 30min in an argon protection environment to obtain a mixed solution.
Wherein: the MXene nano-sheet solution with the concentration of 1mg/mL is prepared by mixing MXene nano-sheets with deionized water according to the proportion of 1:3 (g/g) and uniformly mixing the obtained solution.
The PEI solution with the mass fraction of 3.5wt% is prepared by mixing PEI and deionized water according to the weight ratio of 1:7 mass ratio (g/g) of the mixture.
And thirdly, carrying out suction filtration on the mixed solution on a PTFE filter membrane with the thickness of 50mm and the aperture of 0.22um by a vacuum filter device, and drying for 2-8 hours at room temperature to obtain the MXene@PEI membrane.
Fourthly, spin-coating the ionic liquid IL with different concentrations on the upper surface of the MXene@PEI film by using a spin coater, wherein the mass ratio (g/g) of the MXene@PEI film to the ionic liquid IL is 1: 1.2-1: 2.1. drying for 8 hours at room temperature, and then drying for 24 hours in a vacuum oven at 45 ℃ to obtain a series of MXene@PEI/IL films.
Wherein: the ionic liquid IL refers to 1-vinyl-3-ethylimidazole tetrafluoroborate.
Example 1a method for preparing a high performance mxene@pei/IL film comprising the steps of:
adopting an in-situ etching method to prepare a single-layer two-dimensional MXene nano sheet:
1.6g LiF was dissolved in a PTFE beaker containing 20mL of HCl (8M) and magnetically stirred for 5min; slowly adding 1g of MAX powder into a PTFE beaker containing the mixed solution, stirring for 24 hours at the constant temperature of 45 ℃, and centrifuging at 3500r/min to obtain a precipitate; washing the precipitate with 1M HCl for several times, and then with deionized water for several times until the pH is > 7; finally, the obtained precipitate is subjected to ultrasonic treatment for 20 min under the protection of argon, and is centrifuged for 1 h by 3500r/min, so that the single-layer two-dimensional MXene nano-sheet is obtained.
Mixing 3mL of single-layer two-dimensional MXene nanosheet solution with the concentration of 1mg/mL and 2mL of PEI solution with the mass concentration of 3.5 and wt%, magnetically stirring for 30min in an argon protection environment, enabling the surfaces of the MXene nanosheets to have different charges by utilizing the interaction between molecules, and modifying the surfaces of the MXene nanosheets to obtain a mixed solution.
And thirdly, filtering the mixed solution on a PTFE filter membrane with the thickness of 50mm and the pore diameter of 0.22um by a vacuum filter device, and drying for 8 hours at room temperature to obtain the MXene@PEI membrane.
2mL of ionic liquid IL (20 wt%,25wt%,30wt%,35 wt%) of different concentrations was spin-coated on the upper surface of the MXene@PEI film using a spin coater, spin-coated at 1000 rpm for 10 s, and dried at 3000 rpm for 20 s. Spin-on IL can increase the filter membrane to CO 2 The affinity of the gas is beneficial to improving the selectivity of the gas. Spin-coating with the same volume of IL 5 timesAnd then drying for 8 hours at room temperature, and then drying for 24 hours in a vacuum oven at 45 ℃ to obtain a series of MXene@PEI/IL films.
[ test of different IL loadings vs. MXene@PEI/IL Membrane separation Performance ]
Flatly laying MXene@PEI/IL membranes with different IL loadings prepared in example 1 on a gas permeation tester, generating pressure difference at 25 ℃ and 1bar on two sides of the membrane by using a vacuum pump, making a lower cavity be vacuum under the action of the vacuum pump, and making mixed gas CO under the pushing of pressure 2 /N 2 And CO 2 /CH 4 And finally, introducing the passed gas into a chromatograph for analysis through an MXene@PEI/IL membrane to obtain the corresponding permeability.
Test results: the MXene@PEI/IL membrane prepared by the method is prepared in mixed gas CO 2 /N 2 And CO 2 /CH 4 The separation properties of (a) are shown in figures 2a, b. As can be seen from FIG. 2, the permeability and selectivity of the MXene@PEI/IL membrane changed significantly with increasing IL loading, probably due to the IL vs. CO 2 And the affinity of the MXene@PEI/IL membrane to CO 2 Has high permeability to CO 2 /N 2 And CO 2 /CH 4 Has good selectivity. As the IL loading increases, the upper surface of the membrane becomes smooth and dense, and the increase in membrane thickness lengthens the diffusion path of the gas molecules, ultimately resulting in a decrease in gas permeability. As can be seen from fig. 2a, CO increases with IL loading 2 Has excellent separation performance when IL load is 25wt%, and the MXene@PEI/IL membrane has excellent separation performance on CO 2 /N 2 The maximum transparency of (2) is 5302 GPU and the selectivity is 35.30. At the same time, for CO 2 /CH 4 The maximum transmission of (2) is 436.78 GPU with a selectivity of 32.13. However, as the IL loading increases, the selectivity of the gas increases and then decreases, mainly due to the fact that at lower IL loadings, the membrane itself has some drawbacks, resulting in a relatively low selectivity.
The high permeability and selectivity are due to the fact that the two-dimensional layered MXene nano-sheets provide nano-flow channels for gas separation, which is beneficial to the transportation of gas molecules, and secondly, IL is beneficial to CO 2 Has a certain affinity, is beneficial to CO 2 Is transmitted by the mobile station. Finally, the prepared MXene@PEI/IL membrane has high separation performance.
Thermal stability test for gas separation Using MXene@PEI/IL membranes with an IL loading of 25 wt.% as an example
The separation performance of the MXene@PEI/IL membrane prepared in example 1 with the IL loading amount of 25wt% was tested at different temperatures under the conditions that the pressure was 1bar and the temperature was 25-55 ℃.
Test results: the prepared MXene@PEI/IL film with the IL loading amount of 25wt% is prepared in gas mixture CO 2 /N 2 And CO 2 /CH 4 The thermal stability of (a) is shown in figures 3a, b. As can be seen from FIG. 3, the MXene@PEI/IL membrane pair CO as the temperature increases 2 From 481.78 GPU at 25 ℃, 677.63 GPU at 35 ℃, 738.02 GPU at 45 ℃ to 872.20 GPU at 55 ℃, possibly due to the increase in temperature, the free volume of the MXene@PEI/IL film increases, facilitating the transport of gas molecules. At the same time, CO 2 /N 2 The selectivity was slightly reduced, probably due to N 2 And CH (CH) 4 Permeability ratio of CO 2 The increase is fast, resulting in a gradual decrease of the separation factor (fig. 3a, b).
The temperature rise not only accelerates the dynamic diffusion of gas molecules, resulting in enhanced permeation, but also facilitates N 2 And CH (CH) 4 Flexible rotation and overlap of molecules, allowing more N 2 And CH (CH) 4 Molecular permeation results in reduced selectivity. In addition, as the temperature increases, CO 2 /CH 4 Mixture gas and CO 2 /N 2 The mixture gas has a similar tendency to separate.
In summary, the permeability and selectivity of the MXene@PEI/IL membrane were slightly changed under different temperature tests, indicating that the prepared MXene@PEI/IL membrane has good thermal stability.
Durability test for gas separation with an MXene@PEI/IL membrane having an IL loading of 25 wt.% as an example
The separation performance of the MXene@PEI/IL membrane prepared in example 1 was measured at 25℃under 1bar test conditions on a gas permeation meter for 50 hours.
Test results: the prepared MXene@PEI/IL film with the IL loading amount of 25wt% is prepared in gas mixture CO 2 /N 2 And CO 2 /CH 4 See fig. 4a, b. As can be seen from FIG. 4, the permeability and selectivity of the MXene@PEI/IL membrane fluctuated over a relatively small range in a continuous 50h test. This indicates that the MXene@PEI/IL film has good durability in practical CO 2 Has wide application prospect in separation.
Performance comparison of gas separation by taking an MXene@PEI/IL membrane with an IL loading of 25wt% as an example
The performance of the mxene@pei/IL membrane prepared in example 1 with an IL loading of 25wt% was compared to other reported gas separation membranes at 25 ℃,1 bar.
Test results: the prepared MXene@PEI/IL film with the IL loading amount of 25wt% is prepared in gas mixture CO 2 /N 2 And CO 2 /CH 4 The comparison of the performance of (c) is shown in figure 5. As can be seen from the figure, the prepared MXene@PEI/IL membrane has excellent permeability while maintaining proper selectivity, and can meet the requirement (permeability) of a high flux membrane>1000, selectivity>20 Such high performance is advantageous for industrial applications to meet industrial high throughput requirements.

Claims (7)

1. A preparation method of a high-performance MXene@PEI/IL film comprises the following steps:
preparation of two-dimensional layered Ti by in-situ etching 3 C 2 T x mXene nanoplatelets:
LiF and HCl at 8M were mixed at 1: 11-12.5 mass to volume ratio is added into a magnetically stirred PTFE beaker; slowly adding MAX powder into a PTFE beaker containing the mixed solution, stirring at a constant temperature of 45 ℃ for 24 hours, and centrifuging to obtain a precipitate; the precipitate was washed several times up to pH>7, the time is up to 7; finally, the obtained precipitate is subjected to ultrasonic stripping and centrifugation to obtain single-layer two-dimensional Ti 3 C 2 T x An MXene nanoplatelet solution; the mass ratio of the MAX powder to the LiF is 1:1.8;
mixing an MXene nanosheet solution with the concentration of 1mg/mL and a PEI solution with the mass fraction of 3.5wt%, and magnetically stirring for 30min in an argon protection environment to obtain a mixed solution;
thirdly, carrying out suction filtration on the mixed solution on a polytetrafluoroethylene filter membrane through a vacuum filter device, and drying for 2-8 hours at room temperature to obtain an MXene@PEI membrane;
and fourthly, spin-coating ionic liquid IL with different concentrations on the upper surface of the MXene@PEI film by using a spin-coating machine, drying for 8 hours at room temperature, and then drying for 24 hours in a vacuum oven at 45 ℃ to obtain a series of MXene@PEI/IL films.
2. The method for preparing the high-performance MXene@PEI/IL film according to claim 1, which is characterized by comprising the following steps: in the step (II), the MXene nano-sheet solution with the concentration of 1mg/mL is prepared by mixing MXene nano-sheets with deionized water according to a ratio of 1:3, and uniformly mixing the obtained solution.
3. The method for preparing the high-performance MXene@PEI/IL film according to claim 1, which is characterized by comprising the following steps: the PEI solution with the mass fraction of 3.5wt% in the step (II) is prepared by mixing PEI and deionized water according to a weight ratio of 1:7 mass ratio of the mixture to the solution obtained by uniform mixing.
4. The method for preparing the high-performance MXene@PEI/IL film according to claim 1, which is characterized by comprising the following steps: in the step (II), the mass ratio of the MXene nano-sheet solution to the PEI solution is 3: 2-7.
5. The method for preparing the high-performance MXene@PEI/IL film according to claim 1, which is characterized by comprising the following steps: and in the step III, the thickness of the PTFE filter membrane is 50mm, and the pore diameter is 0.22um.
6. The method for preparing the high-performance MXene@PEI/IL film according to claim 1, which is characterized by comprising the following steps: in the step, the mass ratio of the MXene@PEI film to the ionic liquid IL is 1: 1.2-1: 2.1.
7. the method for preparing the high-performance MXene@PEI/IL film according to claim 1, which is characterized by comprising the following steps: in the step, the ionic liquid IL refers to 1-vinyl-3-ethylimidazole tetrafluoroborate.
CN202310114511.5A 2023-02-15 2023-02-15 Preparation method of high-performance MXene@PEI/IL film Pending CN116173745A (en)

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