Fluorine-containing ionic liquid-mof composite material, and preparation method and application thereof

Abstract

The application discloses a kind of fluorine-containing ionic liquid@MOF composite material and its preparation method and application, belong to functional composite material technical field.The fluorine-containing ionic liquid@MOF composite material is prepared by the specific fluorine-containing ionic liquid being loaded on the surface and pore of MOF by microwave-assisted process in the application, and the preparation condition is mild controllable, energy consumption is reduced by more than 30% than traditional process, and the green environmental protection performance is outstanding.The composite material retains the MOF crystal structure and porous characteristics, so that the ionic liquid is uniformly dispersed on the surface and in the pore of MOF, the loading capacity is increased by more than 20% than traditional stirring method, and the thermal stability is excellent, with the advantages of high ionic conductivity of ionic liquid and high specific surface area of MOF, and shows excellent performance in the field of CO2 selective adsorption and separation.

Description

Technical Field

[0001] This invention belongs to the field of functional composite materials technology. Specifically, it relates to a fluorine-containing ionic liquid@MOF composite material, its preparation method, and its application. Background Technology

[0002] With increasing attention paid to carbon emission control, carbon dioxide emissions from industrial production processes have become a significant issue in the environmental and resource sectors. The CO2 concentration in flue gas emitted from coal-fired power plants, the steel, and cement industries is typically 10%–15%, accompanied by H2O, SO2, and NO. x Against this backdrop, the efficient capture and rational utilization of carbon dioxide in industrial waste gas has become a key technological direction for achieving emission reduction and resource recycling. Therefore, developing novel capture materials that combine high adsorption performance, structural stability, and economic efficiency has become a focus of current research and application.

[0003] Ionic liquids, as a novel green solvent, are considered highly promising green capture media due to their high solubility for CO2 and tunable structure. However, existing ionic liquids suffer from problems such as easy flow, difficulty in immobilization and recovery, and high volatility at high temperatures, which greatly limit their industrial-scale application. Metal-organic frameworks (MOFs) are a class of porous crystalline materials formed by the coordination of metal ions / metal clusters with organic ligands. They possess characteristics such as large specific surface area, regular pore structure, strong designability, and good thermal stability, making them ideal carrier materials for loading ionic liquids. Currently, the construction of ionic liquid@MOF composites by combining ionic liquids and MOFs leverages the porous structure of MOFs to achieve immobilization and structural stability of ionic liquids, overcoming the drawback of easy flow. Simultaneously, combining the synergistic advantages of both enhances the catalytic activity, adsorption selectivity, and ion conductivity of the material, potentially ensuring high CO2 adsorption capacity in high-temperature, high-humidity, or complex waste gas environments. However, current ionic liquid@MOF composites, using ionic liquids as raw materials, suffer from poor thermal stability and electrical conductivity.

[0004] Furthermore, existing methods for preparing ionic liquid@MOF composites mostly employ traditional water bath heating and room temperature stirring impregnation methods. Patent application CN118416857A discloses a novel method for preparing IL@MOF composites, which involves loading the ionic liquid IL onto MOFs using room temperature stirring. However, the disclosed techniques suffer from high energy consumption, long reaction cycles, and poor composite material performance. Traditional stirring loading easily leads to uneven dispersion and local aggregation of the ionic liquid, and the bonding between the ionic liquid and MOF is only physical adsorption, resulting in weak adhesion and easy detachment during use. Additionally, high temperatures or prolonged reactions can damage the MOF crystal framework, leading to impaired porous structure and reduced specific surface area. Poor process controllability and difficulty in precisely controlling the ionic liquid loading further affect the adsorption, catalytic, and electrochemical performance of the composite material, limiting its application in high-temperature and high-precision environments. Summary of the Invention

[0005] To address the problems of high energy consumption, long reaction cycles, poor controllability of loading, easy damage to the MOF crystal framework, and insufficient long-term stability due to poor bonding between ionic liquids and MOFs in existing preparation processes, this invention provides a fluorine-containing ionic liquid@MOF composite material, its preparation method, and its application. This invention uses a microwave-assisted loading method to load a fluorine-containing ionic liquid onto a MOF as a carrier to obtain the fluorine-containing ionic liquid@MOF composite material.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows.

[0007] The first objective of this invention is to provide a fluorine-containing ionic liquid@MOF composite material, which is obtained by mixing a fluorine-containing ionic liquid and a MOF in a solvent, and then loading the ionic liquid onto the surface and pores of the MOF using a microwave-assisted loading method.

[0008] The conditions for the microwave-assisted load method are: microwave power of 100W to 250W, temperature of 60℃ to 80℃, and microwave radiation time of 30min to 1h.

[0009] The fluorinated ionic liquid is 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethylpyridinium bis(fluorosulfonyl)imide, 1-butylpyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium hexafluorophosphate, or 1-butyl-3-methylimidazolium hexafluorophosphate.

[0010] In a preferred embodiment, the microwave is radiated intermittently, with the intermittent radiation method being radiating for 8 minutes followed by a 4-minute interval.

[0011] In a preferred embodiment, the mass ratio of the fluorinated ionic liquid to the MOF is 0.5 to 3:1.

[0012] The second objective of this invention is to provide a method for preparing a fluorine-containing ionic liquid@MOF composite material, comprising the following steps: Fluorine-containing ionic liquids were obtained by mixing equimolar amounts of bromide salt and fluorinated sulfonyl imide lithium salt and carrying out a metathesis reaction at 20℃~45℃ under the action of a first microwave.

[0013] The fluorine-containing ionic liquid and MOF are mixed in a solvent, and the ionic liquid is loaded onto the surface and pores of the MOF under microwave radiation at 60℃~80℃ to obtain a fluorine-containing ionic liquid@MOF composite material.

[0014] In a preferred embodiment, the power of the first microwave is 100W to 300W, and the first microwave radiation lasts for 10 minutes with a 5-minute interval.

[0015] As a preferred embodiment, the preparation method of the MOF includes the following steps: mixing zinc acetate dihydrate with an organic ligand in an organic solvent and carrying out a coordination reaction under the action of a second microwave.

[0016] In a preferred embodiment, when the MOF is MOF-5, the power of the second microwave is 200W to 400W, the temperature is 80℃ to 100℃, and the reaction lasts for 1h to 2h. Alternatively, when the MOF is ZIF-8, the power of the second microwave is 150W to 350W, the temperature is 60℃ to 80℃, and the reaction lasts for 1h to 3h.

[0017] In a preferred embodiment, the solvent is ethylene glycol or dichloromethane.

[0018] The third objective of this invention is to provide an application of fluorine-containing ionic liquid@MOF composite material as a CO2 adsorbent for capturing CO2 gas in industrial waste gas. The application includes the following steps: placing the fluorine-containing ionic liquid@MOF composite material in industrial waste gas and adsorbing CO2 gas in the industrial waste gas at 25°C and 1 atm.

[0019] In a preferred embodiment, the ratio of the fluorinated ionic liquid@MOF composite material to industrial waste gas is 1g:5L~50L.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a fluorine-containing ionic liquid@MOF composite material, which is obtained by loading a fluorine-containing ionic liquid onto the surface and pores of a MOF using a microwave-assisted loading method.

[0021] The fluorine-containing ionic liquid@MOF composite material of this invention utilizes a microwave-assisted loading method. Using MOF as a carrier, a specific fluorine-containing ionic liquid is loaded onto the surface and pores of the MOF. Simultaneously, the uniform heating and molecular polarization of the microwave field effectively ensure the integrity of the composite material structure, perfectly preserving the original crystal structure, porous characteristics, and high specific surface area of ​​the MOF, thereby contributing to improved CO2 adsorption capacity. This invention leverages the porous structure of MOF to achieve immobilization and structural stability of the ionic liquid, while also possessing the high ionic conductivity of the fluorine-containing ionic liquid. The microwave-assisted process enables a stronger interaction between the fluorine-containing ionic liquid and the pores and surface of the MOF, effectively suppressing ionic liquid volatilization and increasing the loading capacity by more than 20% compared to traditional stirring methods. Furthermore, the preparation conditions are mild and controllable, significantly shortening the reaction cycle, reducing energy consumption by more than 30% compared to traditional processes, exhibiting outstanding green and environmentally friendly performance, strong equipment versatility, and ease of industrial-scale production.

[0022] The fluorine-containing ionic liquid@MOF composite material prepared in this invention was placed in industrial waste gas and CO2 was adsorbed at 25℃ and 1 atm. The CO2 adsorption capacity was 4.8 mmol / g to 5.2 mmol / g, which is 15.6% to 20.0% higher than that of traditional MOF-based materials, demonstrating excellent performance in CO2 adsorption and separation. The fluorine-containing ionic liquid@MOF composite material prepared in this invention was also applied to solid electrolytes. An electrolyte was prepared using BMIPF6@MOF-5, and the ionic conductivity at 25℃ was 1.86 × 10⁻⁶. -5 With an S / cm, the ionic conductivity is increased to 180% compared to the polyoxyethylene-lithium hexafluorophosphate (PEO-LiPF6) electrolyte, the electrochemical stability window is 4.8V, and the thermal decomposition temperature is 269℃. Its overall performance is superior to that of pure PEO-LiPF6 electrolyte. Attached Figure Description

[0023] Figure 1 The images show X-ray diffraction patterns of the fluorinated ionic liquids @MOF-5 obtained in Examples 1-12 and @ZIF-8 obtained in Examples 22-23 of this invention, as well as MOF-5 and ZIF-8. Figure 1 a shows the XRD comparison of four ionic liquid @MOF composite materials, namely EMIFSI@MOF-5, EMITFSI@MOF-5, BMIFSI@MOF-5, and BMITFSI@MOF-5, with MOF-5; Figure 1 b is PY 14 FSI@MOF-5, PY14 TFSI@MOF-5, PY 04 FSI@MOF-5, PY 04 TFSI@MOF-5, PY 02 FSI@MOF-5, PY 02 XRD comparison of TFSI@MOF-5 composites of six fluorine-containing ionic liquids@MOF and MOF-5; Figure 1 c is an XRD comparison diagram of four fluorine-containing ionic liquid @MOF composite materials, namely BMIPF6@ZIF-8, EMIPF6@ZIF-8, EMIPF6@MOF-5, and BMIPF6@MOF-5, with ZIF-8 and MOF-5.

[0024] Figure 2 The images show the infrared spectra of the fluorinated ionic liquids @MOF-5 obtained in Examples 1 to 11 and @ZIF-8 obtained in Examples 22 to 23 of this invention, as well as MOF-5 and ZIF-8. Figure 2 a shows the infrared spectra of four fluorine-containing ionic liquid @MOF composite materials, namely EMIFSI@MOF-5, EMITFSI@MOF-5, BMIFSI@MOF-5, and BMITFSI@MOF-5, and MOF-5. Figure 2 b is PY 14 FSI@MOF-5, PY 14 TFSI@MOF-5, PY 04 FSI@MOF-5, PY 04 TFSI@MOF-5, PY 02 FSI@MOF-5, PY 02 Infrared spectra of six fluorine-containing ionic liquids@MOF composite materials and MOF-5; Figure 2 c shows the infrared spectra of four fluorinated ionic liquid @MOF composite materials: BMIPF6@ZIF-8, EMIPF6@ZIF-8, EMIPF6@MOF-5, and BMIPF6@MOF-5, along with ZIF-8 and MOF-5.

[0025] Figure 3 The images show SEM images of MOF-5 and the fluorine-containing ionic liquid @MOF-5 obtained in Examples 11 to 14 of this invention. Figure 3 a is the SEM image of BMIPF6@MOF-5; Figure 3 b is the SEM image of BMIPF6 @ZIF-8; Figure 3 c: SEM image of EMIPF6@MOF-5; Figure 1 d is the SEM image of EMIPF6@ZIF-8; Figure 3e is the SEM image of EMIFSI@MOF-5; Figure 3 f is the SEM image of MOF-5.

[0026] Figure 4 The images show the DSC curves of the fluorinated ionic liquid@MOF composite materials obtained in Examples 4 and 10 of this invention, and the fluorinated ionic liquid@ZIF-8 obtained in Examples 22 and 23, compared with MOF-5 and ZIF-8. Figure 4 a is a comparison chart of the DSC curves of EMITFSI, EMITFSI@MOF-5 and MOF-5; Figure 4 b is PY 14 TFSI and PY 14 Comparison of DSC curves between TFSI@MOF-5 and MOF-5; Figure 4 c is a comparison chart of DSC curves for BMIPF6@ZIF-8, EMIPF6@ZIF-8, EMIPF6@MOF-5, BMIPF6@MOF-5, and ZIF-8 and MOF-5.

[0027] Figure 5 Thermogravimetric (TG) analysis diagrams of MOF materials, the BMIPF6@ZIF-8 composite material obtained in Example 22, and the EMIFSI@MOF-5 composite material obtained in Example 1. Detailed Implementation

[0028] To enable those skilled in the art to better understand and implement the technical solutions of this invention, the invention is further described below with reference to specific embodiments. However, the embodiments are not intended to limit the invention. Unless otherwise specified, the following test methods and detection methods are conventional methods; unless otherwise specified, the reagents and raw materials are commercially available.

[0029] Existing methods for preparing ionic liquid@MOF composites mostly employ traditional water bath heating and room temperature stirring impregnation. Patent application CN118416857A discloses a novel method for preparing IL@MOF composites, which involves loading the ionic liquid IL onto MOFs at room temperature with stirring. However, the disclosed techniques suffer from high energy consumption, long reaction cycles, and poor composite material performance. Traditional stirring loading easily leads to uneven dispersion and local aggregation of the ionic liquid, and the bonding between the ionic liquid and MOF is only physical adsorption, resulting in weak adhesion and easy detachment during use. Furthermore, high temperatures or prolonged reactions can damage the MOF crystal framework, leading to impaired porous structure and reduced specific surface area. The process controllability is poor, and the ionic liquid loading is difficult to precisely control, thus affecting the adsorption, catalytic, and electrochemical performance of the composite material and limiting its application in high-temperature, high-precision environments. Based on these problems, this invention provides a fluorine-containing ionic liquid@MOF composite material, its preparation method, and its applications.

[0030] The technical solution of the present invention will be analyzed in detail below.

[0031] This invention provides a fluorine-containing ionic liquid@MOF composite material, which is obtained by mixing a fluorine-containing ionic liquid and a MOF in a solvent, and then loading the ionic liquid onto the surface and pores of the MOF using a microwave-assisted loading method.

[0032] The conditions for the microwave-assisted loading method are: microwave reactor power of 100W to 250W, reaction temperature of 60℃ to 80℃, and intermittent radiant stirring for 30min to 1h.

[0033] The fluorinated ionic liquid is 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethylpyridinium bis(fluorosulfonyl)imide, 1-butylpyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium hexafluorophosphate, or 1-butyl-3-methylimidazolium hexafluorophosphate.

[0034] In the above technical solution, a fluorinated ionic liquid@MOF composite material is prepared by loading a specific fluorinated ionic liquid onto the surface and pores of a MOF. Through microwave-assisted processing, reaction parameters are precisely controlled, resulting in mild and controllable preparation conditions, energy consumption reduced by more than 30% compared to traditional processes, and no harmful byproducts generated, demonstrating outstanding green and environmentally friendly performance. Simultaneously, the microwave method significantly shortens the reaction cycle (overall time reduced by 40%–50% compared to traditional processes), with simple and controllable process steps, strong equipment versatility, and easy industrial-scale production. The process involves synthesizing the fluorinated ionic liquid through a microwave-assisted metathesis reaction, preparing the MOF support using a microwave method, and then composited with the MOF support using a microwave-assisted loading method. This strengthens the interaction between the fluorinated ionic liquid and the MOF, perfectly preserving the original crystal structure and porous characteristics of the MOF, ensuring uniform dispersion of the fluorinated ionic liquid on the MOF surface and within the pores, and increasing the loading capacity by more than 20% compared to traditional stirring methods. It combines the high ionic conductivity of the fluorinated ionic liquid with the high specific surface area of ​​the MOF, exhibiting excellent thermal stability, thus demonstrating superior performance in the fields of selective CO2 adsorption and separation and solid-state electrolytes for lithium-ion batteries.

[0035] The technical solution of the present invention will be further illustrated below through the following embodiments and comparative examples.

[0036] Example 1 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid EMIFSI: In a 100 mL microwave-safe reactor, 80 mmol of lithium bis(fluorosulfonyl)imide (LiFSI) and 80 mmol of 1-butyl-3-methylimidazolium bromide (EMIBr) were added, followed by 4 mL of distilled water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 25 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min radiation / 5 min interval) for 8 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ion residue remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 3 h to obtain the EMIFSI ionic liquid.

[0037] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF (dimethylformamide) and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0038] Preparation of S3, EMIFSI@MOF-5 composite material: Weigh 1g MOF-5 and 2g EMIFSI, add 10mL ethylene glycol, and place in a microwave reactor. Set the microwave power to 180W and the temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote rapid penetration of EMIFSI into the pores and surface of MOF-5. After the reaction, centrifuge the mixture at 7000r / min for 10min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and vacuum dry at 80℃ for 2h to obtain the EMIFSI@MOF-5 composite material.

[0039] Example 2 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid BMITFSI: In a 100 mL microwave-safe reactor, 28 mmol of lithium bis(trifluoromethanesulfonylimide) (LiTFSI) and 28 mmol of 1-ethyl-3-methylimidazolium bromide (BMIBr) were added, along with 4 mL of deionized water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 20 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min of radiation / 5 min of intermittent irradiation) for 6 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 2.5 h to obtain the BMITFSI ionic liquid.

[0040] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0041] Preparation of S3, BMITFSI@MOF-5 composite material: Weigh 1g MOF and 2g BMITFSI, add 10mL ethylene glycol, and place in a microwave reactor. Set the microwave power to 180W and the temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote rapid penetration of BMITFSI into the pores and surface of MOF. After the reaction, centrifuge the mixture at 7000r / min for 10min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and vacuum dry at 80℃ for 2h to obtain the BMITFSI@MOF-5 composite material.

[0042] Example 3 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid BMIFSI: In a 100 mL microwave-safe reactor, 50 mmol of lithium difluorosulfonylimide (LiFSI) and 50 mmol of 1-ethyl-3-methylimidazolium bromide (BMIBr) were added, along with 4 mL of distilled water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 20 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min radiation / 5 min interval) for 6 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 2 h to obtain the BMIFSI ionic liquid.

[0043] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0044] Preparation of S3, BMIFSI@MOF-5 composite material: Weigh 1g MOF and 2g BMIFSI, add 10mL ethylene glycol, and place in a microwave reactor. Set the microwave power to 180W and the temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote rapid penetration of BMIFSI into the pores and surface of MOF. After the reaction, centrifuge the mixture at 7000r / min for 10min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and vacuum dry at 80℃ for 2h to obtain the BMIFSI@MOF-5 composite material.

[0045] Example 4 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid EMITFSI: In a 100 mL microwave-safe reactor, 60 mmol of lithium bis(trifluoromethanesulfonylimide) (LiTFSI) and 60 mmol of 1-butyl-3-methylimidazolium bromide (EMIBr) were added, along with 4 mL of distilled water and 60 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 20 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min radiation / 5 min interval) for 6 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 3 h to obtain the EMITFSI ionic liquid.

[0046] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0047] Preparation of S3, EMITFSI@MOF composite material: Weigh 1g MOF and 2g EMITFSI, add 10mL ethylene glycol, and place in a microwave reactor. Set the microwave power to 180W and the temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote the rapid penetration of EMITFSI into the pores and surface of MOF. After the reaction, centrifuge the mixture at 7000r / min for 10min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and vacuum dry at 80℃ for 2h to obtain EMITFSI@MOF-5 composite material.

[0048] Example 5 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1, fluorine-containing ionic liquid PY 02 Synthesis of FSI: In a 100 mL microwave-safe reactor, 0.05 mol of lithium bis(fluorosulfonyl)imide (LiFSI) and 0.05 mol of 1-butylpyridine bromide (PY) were added. 02 Add 4 mL of deionized water and 26 mL of anhydrous dichloromethane to the bromine solution (Br), stir well, and place in a microwave reactor. Set the microwave power to 200 W, control the reaction temperature at 25 °C, and use intermittent radiation mode (10 min radiation / 5 min interval) for 10 h. After the reaction, transfer to a separatory funnel to separate the layers. Wash the organic phase repeatedly with distilled water until no bromide ions remain (no white precipitate is formed upon addition of silver nitrate solution to the upper aqueous phase). Remove dichloromethane by rotary evaporation at 60 °C, and dry under reduced pressure at 60 °C to obtain PY. 02 FSI ionic liquids.

[0049] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0050] S3, PY 02 Preparation of FSI@MOF composite material: Weigh 1g MOF-5 and 2g PY02FSI, add 10mL ethylene glycol, and place in a microwave reactor. Set microwave power to 180W, temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote the reaction of PY02FSI. 02 FSI rapidly penetrated into the pores and surface of the MOF. After the reaction was complete, the mixture was centrifuged at 7000 rpm for 10 min, the precipitate was collected, washed three times with acetone to remove residual solvent, and dried under vacuum at 80 °C for 2 h to obtain PY. 02 FSI@MOF-5 composite material.

[0051] Example 6 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1, fluorine-containing ionic liquid PY 02 Synthesis of TFSI: In a 100 mL microwave-safe reactor, 0.03 mol LiTFSI and 0.03 mol 1-ethylpyridine bromide (PY) were added. 02 Add 4 mL of deionized water and 26 mL of anhydrous dichloromethane to the bromine solution (Br), stir well, and place in a microwave reactor. Set the microwave power to 200 W, control the reaction temperature at 25 °C, and use intermittent radiation mode (10 min radiation / 5 min interval) for 10 h. After the reaction, transfer to a separatory funnel to separate the layers. Wash the organic phase repeatedly with distilled water until no bromide ions remain (no white precipitate is formed upon addition of silver nitrate solution to the upper aqueous phase). Remove dichloromethane by rotary evaporation at 60 °C, and dry under reduced pressure at 60 °C to obtain PY. 02 TFSI ionic liquid.

[0052] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0053] S3, PY 02 Preparation of TFSI@MOF composite material: Weigh 1g MOF and 2g PY 02 Add 10 mL of TFSI and ethylene glycol to a microwave-safe reactor. Set the microwave power to 180 W and the temperature to 70 °C. Use intermittent radiative stirring mode (8 min radiative stirring / 4 min intermittent stirring) for 45 min to promote the reaction of PY. 02 TFSI rapidly penetrated into the pores and surface of MOF. After the reaction, the mixture was centrifuged at 7000 r / min for 10 min, the precipitate was collected, washed three times with acetone to remove residual solvent, and dried under vacuum at 80℃ for 2 h to obtain PY. 02 TFSI@MOF-5 composite material.

[0054] Example 7 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1, fluorine-containing ionic liquid PY 04 Synthesis of FSI: 0.05 mol LiFSI and 0.05 mol PY were added to a 100 mL microwave-safe reactor. 04 Br was added to 4 mL of deionized water and 26 mL of anhydrous dichloromethane, and the mixture was stirred thoroughly before being placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and an intermittent radiation mode was used (10 min of radiation followed by 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY. 04 FSI ionic liquids.

[0055] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0056] S3, PY 04 Preparation of FSI@MOF composite material: Weigh 1g MOF and 2g PY 04 Add 10 mL of ethylene glycol to FSI and place in a microwave-safe reactor. Set the microwave power to 180 W and the temperature to 70 °C. Use intermittent radiative stirring mode (8 min radiative stirring / 4 min intermittent stirring) and react for 45 min to promote the reaction of PY. 04 FSI rapidly penetrated into the pores and surface of MOF. After the reaction, the mixture was centrifuged at 7000 r / min for 10 min, the precipitate was collected, washed three times with acetone to remove residual solvent, and dried under vacuum at 80℃ for 2 h to obtain PY. 04 FSI@MOF-5 composite material.

[0057] Example 8 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1, fluorine-containing ionic liquid PY 04 Synthesis of TFSI: 0.03 mol LiTFSI and 0.03 mol PY were added to a 100 mL microwave-safe reactor. 04 Br was added to 4 mL of deionized water and 26 mL of anhydrous dichloromethane, and the mixture was stirred thoroughly before being placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and an intermittent radiation mode was used (10 min of radiation followed by 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY. 04 TFSI ionic liquid.

[0058] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0059] S3, PY 04 Preparation of TFSI@MOF composite material: Weigh 1g MOF and 2g PY 04 Add 10 mL of TFSI and ethylene glycol to a microwave-safe reactor. Set the microwave power to 180 W and the temperature to 70 °C. Use intermittent radiative stirring mode (8 min radiative stirring / 4 min intermittent stirring) for 45 min to promote the reaction of PY. 04 TFSI rapidly penetrated into the pores and surface of MOF. After the reaction, the mixture was centrifuged at 7000 r / min for 10 min, the precipitate was collected, washed three times with acetone to remove residual solvent, and dried under vacuum at 80℃ for 2 h to obtain PY. 04 TFSI@MOF-5 composite material.

[0060] Example 9 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1, fluorine-containing ionic liquid PY 14 FSI synthesis: 0.04 mol LiFSI and 0.04 mol PY were added to a 100 mL microwave-safe reactor. 14 Br was added to 4 mL of deionized water and 26 mL of anhydrous dichloromethane, and the mixture was stirred thoroughly before being placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and an intermittent radiation mode was used (10 min of radiation followed by 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY. 14 FSI ionic liquids.

[0061] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0062] S3, PY 14 Preparation of FSI@MOF composite material: Weigh 1g MOF and 2g PY 14 Add 10 mL of ethylene glycol to FSI and place in a microwave reactor. Set the microwave power to 180 W and the temperature to 70 °C, using intermittent radiative stirring mode (8 min radiative stirring / 4 min intermittent stirring) for 45 min to promote rapid penetration of PY14FSI into the MOF channels and surface. After the reaction, centrifuge the mixture at 7000 r / min for 10 min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and dry under vacuum at 80 °C for 2 h to obtain PY14FSI. 14 FSI@MOF-5 composite material.

[0063] Example 10 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1, fluorine-containing ionic liquid PY 14 Synthesis of TFSI: 0.06 mol LiTFSI and 0.06 mol PY14Br were added to a 100 mL microwave-safe reactor, along with 4 mL deionized water and 26 mL anhydrous dichloromethane. After thorough mixing, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and intermittent radiation mode was used (10 min irradiation / 5 min intermittent irradiation) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ion residue remained (no white precipitate was observed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY14Br. 14 TFSI ionic liquid.

[0064] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0065] S3, PY 14 Preparation of TFSI@MOF composite material: Weigh 1g MOF and 2g PY 14 Add 10 mL of TFSI and ethylene glycol to a microwave-safe reactor. Set the microwave power to 180 W and the temperature to 70 °C. Use intermittent radiative stirring mode (8 min radiative stirring / 4 min intermittent stirring) for 45 min to promote the reaction of PY. 14 TFSI rapidly penetrated into the pores and surface of MOF. After the reaction, the mixture was centrifuged at 7000 r / min for 10 min, the precipitate was collected, washed three times with acetone to remove residual solvent, and dried under vacuum at 80℃ for 2 h to obtain PY. 14 TFSI@MOF-5 composite material.

[0066] Example 11 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1. Synthesis of the fluorine-containing ionic liquid EMIPF6: 8.41 g of EMIBr and 7.36 g of LiPF6 were added to a 100 mL microwave-safe reactor, along with 20 mL of deionized water and 20 mL of anhydrous dichloromethane. After thorough mixing, the mixture was placed in a microwave reactor. The microwave power was set to 250 W, the reaction temperature was controlled at 40 °C, and intermittent radiation mode was used (10 min of radiation / 5 min of intermittent irradiation) for 3 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with deionized water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 45 °C, and the mixture was dried under reduced pressure at 60 °C to obtain the EMIPF6 ionic liquid.

[0067] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0068] Preparation of S3, EMIPF6@MOF composite material: Weigh 1g MOF and 2g EMIPF6, add 10mL ethylene glycol, and place in a microwave reactor. Set the microwave power to 180W and the temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote the rapid penetration of EMIPF6 into the MOF channels and surface. After the reaction, centrifuge the mixture at 7000r / min for 10min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and vacuum dry at 80℃ for 2h to obtain EMIPF6@MOF-5 composite material.

[0069] Example 12 A method for preparing a fluorine-containing ionic liquid@MOF composite material includes the following steps: S1. Synthesis of the fluorine-containing ionic liquid BMIMPF6: In a 100 mL microwave-safe reactor, 9.29 g of BMIBr and 7.36 g of potassium hexafluorophosphate were added, along with 20 mL of deionized water and 20 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 250 W, the reaction temperature was controlled at 40 °C, and an intermittent radiation mode was used (10 min of radiation / 5 min of intermittent reaction) for 3 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with deionized water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain the BMIMPF6 ionic liquid.

[0070] Preparation of S2, MOF-5: 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid were added to a 100 mL microwave-safe reactor, along with 25 mL of DMF and 25 mL of ethanol. 1 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 30 min to allow initial dispersion. The reactor was then placed in a microwave reactor, and the microwave power was set to 300 W and the temperature to 90 °C. The reaction was continued for 1.5 h. After the reaction, the mixture was allowed to cool naturally to room temperature, centrifuged at 3500 r / min for 10 min, and the precipitate was washed three times with DMF and ethanol, respectively. The precipitate was then dried under vacuum at 65 °C for 6 h to obtain a white powdered MOF-5.

[0071] Preparation of S3, BMIMPF6@MOF composite material: Weigh 1g MOF and 2g BMIMPF6, add 10mL ethylene glycol, and place in a microwave reactor. Set the microwave power to 180W and the temperature to 70℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 45min to promote the rapid penetration of BMIMPF6 into the pores and surface of MOF. After the reaction, centrifuge the mixture at 7000r / min for 10min, collect the precipitate, wash the precipitate three times with acetone to remove residual solvent, and vacuum dry at 80℃ for 2h to obtain BMIMPF6@MOF-5 composite material.

[0072] Example 13 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid EMIFSI: In a 100 mL microwave-safe reactor, 80 mmol of lithium bis(fluorosulfonyl)imide (LiFSI) and 80 mmol of 1-butyl-3-methylimidazolium bromide (EMIBr) were added, followed by 4 mL of distilled water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 25 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min radiation / 5 min interval) for 8 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ion residue remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 3 h to obtain the EMIFSI ionic liquid.

[0073] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0074] Preparation of S3, EMIFSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g EMIFSI, add 10mL dichloromethane, and ultrasonically disperse for 30min before transferring to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, using intermittent radiative stirring mode (8min radiative stirring / 4min intermittent stirring) for 60min to enhance the interaction and pore penetration of EMIFSI and ZIF-8. After the reaction, centrifuge the mixture at 8000r / min for 5min, collect the precipitate, wash the precipitate three times with dichloromethane to remove free ionic liquid, and perform gradient drying (45℃ for 0.5h, 65℃ for 1h) to obtain the EMIFSI@ZIF-8 composite material. The ionic liquid loading reached 40%, which is 23% higher than that of the traditional stirring method.

[0075] Example 14 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid BMITFSI: In a 100 mL microwave-safe reactor, 28 mmol of lithium bis(trifluoromethanesulfonylimide) (LiTFSI) and 28 mmol of 1-ethyl-3-methylimidazolium bromide (BMIBr) were added, along with 4 mL of deionized water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 20 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min of radiation / 5 min of intermittent irradiation) for 6 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 2.5 h to obtain the BMITFSI ionic liquid.

[0076] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0077] Preparation of S3, BMITFSI@ZIF-8 composite material: 0.3g ZIF-8 and 0.6g BMITFSI were weighed, and 10mL dichloromethane was added. After ultrasonic dispersion for 30min, the mixture was transferred to a microwave reactor. The microwave power was set to 220W, the temperature to 65℃, and an intermittent radiative stirring mode was used (radiation for 8min / intermittent for 4min). The reaction was carried out for 60min to enhance the interaction between BMITFSI and ZIF-8 and the permeability of the pores. After the reaction, the mixture was centrifuged at 8000r / min for 5min, the precipitate was collected, and the precipitate was washed three times with dichloromethane to remove free ionic liquid. Gradient drying was performed (drying at 45℃ for 0.5h, drying at 65℃ for 1h) to obtain the BMITFSI@ZIF-8 composite material. The ionic liquid loading reached 41%, which is 24% higher than that of the traditional stirring method.

[0078] Example 15 A method for preparing a fluorine-containing ionic liquid@ZIF-8F composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid BMIFSI: In a 100 mL microwave-safe reactor, 50 mmol of lithium difluorosulfonylimide (LiFSI) and 50 mmol of 1-ethyl-3-methylimidazolium bromide (BMIBr) were added, along with 4 mL of distilled water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 20 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min radiation / 5 min interval) for 6 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 2 h to obtain the BMIFSI ionic liquid.

[0079] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0080] Preparation of S3, BMIFSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g BMIFSI, add 10mL dichloromethane, and ultrasonically disperse for 30min before transferring to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, using intermittent radiative stirring mode (8min radiative / 4min intermittent), and react for 60min to enhance the interaction and pore penetration of BMIFSI and ZIF-8. After the reaction, centrifuge the mixture at 8000r / min for 5min, collect the precipitate, wash the precipitate three times with dichloromethane to remove free ionic liquid, and perform gradient drying (45℃ for 0.5h, 65℃ for 1h) to obtain the BMIFSI@ZIF-8 composite material with an ionic liquid loading of 39%, which is 22% higher than that of the traditional stirring method.

[0081] Example 16 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: Synthesis of S1, the fluorine-containing ionic liquid EMITFSI: In a 100 mL microwave-safe reactor, 60 mmol of lithium bis(trifluoromethanesulfonylimide) (LiTFSI) and 60 mmol of 1-butyl-3-methylimidazolium bromide (EMIBr) were added, along with 4 mL of distilled water and 60 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, and the reaction temperature was controlled at 20 °C (microwave-assisted at room temperature). Intermittent radiation mode was used (10 min radiation / 5 min interval) for 6 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C for 3 h to obtain the EMITFSI ionic liquid.

[0082] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0083] Preparation of S3, EMITFSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g EMITFSI, add 10mL dichloromethane, and ultrasonically disperse for 30min before transferring to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, using intermittent radiative stirring mode (radiation for 8min / intermittent for 4min), and react for 60min to enhance the interaction and pore penetration of EMITFSI and ZIF-8. After the reaction, centrifuge the mixture at 8000r / min for 5min, collect the precipitate, wash the precipitate three times with dichloromethane to remove free ionic liquid, and perform gradient drying (drying at 45℃ for 0.5h, drying at 65℃ for 1h) to obtain the EMITFSI@ZIF-8 composite material with an ionic liquid loading of 37%, which is 20% higher than that of the traditional stirring method.

[0084] Example 17 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: S1, fluorine-containing ionic liquid PY 02 Synthesis of FSI: In a 100 mL microwave-safe reactor, 0.05 mol of lithium bis(fluorosulfonyl)imide (LiFSI) and 0.05 mol of 1-butylpyridine bromide (PY) were added. 02 Add 4 mL of deionized water and 26 mL of anhydrous dichloromethane to the bromine solution (Br), stir well, and place in a microwave reactor. Set the microwave power to 200 W, control the reaction temperature at 25 °C, and use intermittent radiation mode (10 min radiation / 5 min interval) for 10 h. After the reaction, transfer to a separatory funnel to separate the layers. Wash the organic phase repeatedly with distilled water until no bromide ions remain (no white precipitate is formed upon addition of silver nitrate solution to the upper aqueous phase). Remove dichloromethane by rotary evaporation at 60 °C, and dry under reduced pressure at 60 °C to obtain PY. 02 FSI ionic liquids.

[0085] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0086] S3, PY 02Preparation of FSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g PY02FSI, add 10mL dichloromethane, ultrasonically disperse for 30min, and then transfer to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, using intermittent radiative stirring mode (radiation for 8min / intermittent for 4min), and react for 60min to strengthen PY. 02 Interaction between FSI and ZIF-8 and pore permeation. After the reaction, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was collected, and the precipitate was washed three times with dichloromethane to remove free ionic liquid. The precipitate was then subjected to gradient drying (45℃ for 0.5 h, 65℃ for 1 h) to obtain PY. 02 The FSI@ZIF-8 composite material has an ionic liquid loading of 36%, which is 19% higher than that of the traditional stirring method.

[0087] Example 18 A method for preparing a fluorine-containing ionic liquid@ZIF-8F composite material includes the following steps: S1, fluorine-containing ionic liquid PY 02 Synthesis of TFSI: In a 100 mL microwave-safe reactor, 0.03 mol LiTFSI and 0.03 mol 1-ethylpyridine bromide (PY) were added. 02 Add 4 mL of deionized water and 26 mL of anhydrous dichloromethane to the bromine-containing organic phase (Br), stir well, and place in a microwave reactor. Set the microwave power to 200 W, control the reaction temperature at 25 °C, and use intermittent radiation mode (10 min radiation / 5 min interval) for 10 h. After the reaction, transfer to a separatory funnel to separate the phases. Wash the organic phase repeatedly with distilled water until no bromide ions remain (no white precipitate is formed upon addition of silver nitrate solution to the upper aqueous phase). Remove the dichloromethane by rotary evaporation at 60 °C, and dry under reduced pressure at 60 °C to obtain PY. 02 TFSI ionic liquid.

[0088] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0089] S3, PY 02 Preparation of TFSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g PY 02TFSI was added to 10 mL of dichloromethane, and after ultrasonic dispersion for 30 min, it was transferred to a microwave reactor. The microwave power was set to 220 W, the temperature to 65 °C, and an intermittent radiative stirring mode was used (8 min radiative stirring / 4 min intermittent stirring) for 60 min to enhance the reaction of PY. 02 Interaction and pore permeation between TFSI and ZIF-8. After the reaction, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was collected, and the precipitate was washed three times with dichloromethane to remove free ionic liquid. The precipitate was then subjected to gradient drying (45℃ for 0.5 h, 65℃ for 1 h) to obtain PY. 02 The TFSI@ZIF-8 composite material has an ionic liquid loading of 38%, which is 21% higher than that of the traditional stirring method.

[0090] Example 19 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: S1, fluorine-containing ionic liquid PY 04 Synthesis of FSI: 0.05 mol LiFSI and 0.05 mol PY were added to a 100 mL microwave-safe reactor. 04 Br was added to 4 mL of deionized water and 26 mL of anhydrous dichloromethane, and the mixture was stirred thoroughly before being placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and an intermittent radiation mode was used (10 min of radiation followed by 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY. 04 FSI ionic liquids.

[0091] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0092] S3, PY 04Preparation of FSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g PY04FSI, add 10mL dichloromethane, ultrasonically disperse for 30min, and then transfer to a microwave reactor. Set microwave power to 220W, temperature to 65℃, and use intermittent radiative stirring mode (radiation for 8min / intermittent for 4min) for 60min to strengthen PY. 04 Interaction between FSI and ZIF-8 and pore permeation. After the reaction, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was collected, and the precipitate was washed three times with dichloromethane to remove free ionic liquid. The precipitate was then subjected to gradient drying (45℃ for 0.5 h, 65℃ for 1 h) to obtain PY. 04 The FSI@ZIF-8 composite material has an ionic liquid loading of 35%, which is 18% higher than that of the traditional stirring method.

[0093] Example 20 A method for preparing a fluorine-containing ionic liquid@ZIF-8F composite material includes the following steps: S1, fluorine-containing ionic liquid PY 04 Synthesis of TFSI: 0.03 mol LiTFSI and 0.03 mol PY were added to a 100 mL microwave-safe reactor. 04 Br was added to 4 mL of deionized water and 26 mL of anhydrous dichloromethane, and the mixture was stirred thoroughly before being placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and an intermittent radiation mode was used (10 min of radiation followed by 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY. 04 TFSI ionic liquid.

[0094] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0095] S3, PY 04 Preparation of TFSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g PY 04TFSI was added to 10 mL of dichloromethane, and after ultrasonic dispersion for 30 min, it was transferred to a microwave reactor. The microwave power was set to 220 W, the temperature to 65 °C, and an intermittent radiative stirring mode was used (8 min radiative stirring / 4 min intermittent stirring) for 60 min to enhance the reaction of PY. 04 Interaction and pore permeation between TFSI and ZIF-8. After the reaction, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was collected, and the precipitate was washed three times with dichloromethane to remove free ionic liquid. The precipitate was then subjected to gradient drying (45℃ for 0.5 h, 65℃ for 1 h) to obtain PY. 04 The TFSI@ZIF-8 composite material has an ionic liquid loading of 42%, which is 25% higher than that of the traditional stirring method.

[0096] Example 21 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: S1, fluorine-containing ionic liquid PY 14 FSI synthesis: 0.04 mol LiFSI and 0.04 mol PY were added to a 100 mL microwave-safe reactor. 14 Br was added to 4 mL of deionized water and 26 mL of anhydrous dichloromethane, and the mixture was stirred thoroughly before being placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and an intermittent radiation mode was used (10 min of radiation followed by 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain PY. 14 FSI ionic liquids.

[0097] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0098] S3, PY 14 Preparation of TFSI@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g PY 14TFSI was added to 10 mL of dichloromethane, and after ultrasonic dispersion for 30 min, it was transferred to a microwave reactor. The microwave power was set to 220 W, the temperature to 65 °C, and an intermittent radiative stirring mode was used (8 min radiative stirring / 4 min intermittent stirring) for 60 min to enhance the reaction of PY. 14 Interaction and pore permeation between TFSI and ZIF-8. After the reaction, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was collected, and the precipitate was washed three times with dichloromethane to remove free ionic liquid. The precipitate was then subjected to gradient drying (45℃ for 0.5 h, 65℃ for 1 h) to obtain PY. 14 The TFSI@ZIF-8 composite material has an ionic liquid loading of 38%, which is 21% higher than that of the traditional stirring method.

[0099] Example 22 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: S1. Synthesis of the fluorine-containing ionic liquid BMIPF6: In a 100 mL microwave-safe reactor, 0.04 mol LiPF6 and 0.04 mol BMIBr were added, along with 4 mL of deionized water and 26 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 200 W, the reaction temperature was controlled at 25 °C, and intermittent radiation mode was used (10 min of radiation / 5 min of intermittent reaction) for 10 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with distilled water until no bromide ions remained (no white precipitate was formed upon addition of silver nitrate solution to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain the BMIPF6 ionic liquid.

[0100] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0101] Preparation of S3, BMIPF6@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g BMIPF6, add 10mL dichloromethane, and ultrasonically disperse for 30min before transferring to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, and intermittently stir for 1h (8min of radiation / 4min of intermittent stirring) to enhance the interaction between the ionic liquid and ZIF-8. Then centrifuge at 8000r / min for 5min, collect the precipitate, wash the precipitate three times with dichloromethane, and perform gradient drying (drying at 45℃ for 0.5h, then drying at 65℃ for 1h) to obtain the BMIPF6@ZIF-8 composite material, which has uniform ionic liquid loading without aggregation.

[0102] Example 23 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: S1. Synthesis of the fluorine-containing ionic liquid EMIPF6: 8.41 g of EMIBr and 7.36 g of LiPF6 were added to a 100 mL microwave-safe reactor, along with 20 mL of deionized water and 20 mL of anhydrous dichloromethane. After thorough mixing, the mixture was placed in a microwave reactor. The microwave power was set to 250 W, the reaction temperature was controlled at 40 °C, and intermittent radiation mode was used (10 min of radiation / 5 min of intermittent irradiation) for 3 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with deionized water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 45 °C, and the mixture was dried under reduced pressure at 60 °C to obtain the EMIPF6 ionic liquid.

[0103] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0104] Preparation of S3, EMIPF6@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g EMIPF6, add 10mL dichloromethane, and ultrasonically disperse for 30min before transferring to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, using intermittent radiative stirring mode (radiation for 8min / intermittent for 4min), and react for 60min to enhance the interaction and pore penetration of EMIPF6 and ZIF-8. After the reaction, centrifuge the mixture at 8000r / min for 5min, collect the precipitate, wash the precipitate three times with dichloromethane to remove free ionic liquid, and perform gradient drying (drying at 45℃ for 0.5h, drying at 65℃ for 1h) to obtain the EMIPF6@ZIF-8 composite material with an ionic liquid loading of 37%, which is 20% higher than that of the traditional stirring method.

[0105] Example 24 A method for preparing a fluorine-containing ionic liquid@ZIF-8 composite material includes the following steps: S1. Synthesis of the fluorine-containing ionic liquid BMIMPF6: 9.29 g of BMIBr and 7.36 g of potassium hexafluorophosphate were added to a 100 mL microwave-safe reactor, along with 20 mL of deionized water and 20 mL of anhydrous dichloromethane. After stirring thoroughly, the mixture was placed in a microwave reactor. The microwave power was set to 250 W, the reaction temperature was controlled at 40 °C, and an intermittent radiation mode was used (10 min of radiation / 5 min of intermittent reaction) for 3 h. After the reaction, the mixture was transferred to a separatory funnel to separate the layers. The organic phase was repeatedly washed with deionized water until no bromide ions remained (no white precipitate was observed when silver nitrate solution was added to the upper aqueous phase). Dichloromethane was removed by rotary evaporation at 60 °C, and the mixture was dried under reduced pressure at 60 °C to obtain the BMIMPF6 ionic liquid. Compared to traditional constant-temperature stirring, microwave-assisted reaction shortened the reaction time by 50% and significantly improved the yield.

[0106] Preparation of S2, ZIF-8: 0.3 g of zinc acetate dihydrate was dissolved in 14 mL of methanol to obtain solution A, and 0.66 g of 2-methylimidazole was dissolved in 14 mL of methanol to obtain solution B. Solution B was slowly poured into solution A, stirred evenly, and then transferred to a microwave reactor. The microwave power was set to 280 W, the temperature to 70 °C, and magnetic stirring was maintained (400 r / min) for 2 h. After the reaction was completed, the mixture was centrifuged at 8000 r / min for 5 min, the precipitate was washed three times with methanol, and dried under vacuum at 90 °C for 6 h to obtain white powder ZIF-8.

[0107] Preparation of S3, BMIPF6@ZIF-8 composite material: Weigh 0.3g ZIF-8 and 0.6g BMIPF6, add 10mL dichloromethane, and ultrasonically disperse for 30min before transferring to a microwave reactor. Set the microwave power to 220W and the temperature to 65℃, using intermittent radiative stirring mode (radiation for 8min / intermittent for 4min), and react for 60min to enhance the interaction and pore penetration of BMIPF6 and ZIF-8. After the reaction, centrifuge the mixture at 8000r / min for 5min, collect the precipitate, wash the precipitate three times with dichloromethane to remove free ionic liquid, and perform gradient drying (drying at 45℃ for 0.5h, then at 65℃ for 1h) to obtain the BMIPF6@ZIF-8 composite material with an ionic liquid loading of 40%, which is 23% higher than that of the traditional stirring method.

[0108] To further illustrate the effects of the present invention, comparative examples are also provided, as follows: Comparative Example 1: Synthesis of EMITFSI ionic liquid using conventional methods.

[0109] S1, in a 100 mL conventional three-necked flask, add 60 mmol of lithium bis(trifluoromethanesulfonylimide) (LiTFSI) and 60 mmol of 1-ethyl-3-methylimidazolium bromide (EMIBr), add 4 mL of distilled water and 60 mL of anhydrous dichloromethane, place on a constant temperature water bath, use mechanical stirring (300 r / min), control the water bath temperature at 20 °C (consistent with the reaction temperature in the example), and continue stirring for 24 h.

[0110] S2. After the reaction is complete, the reaction solution is transferred to a separatory funnel and allowed to stand for separation. The organic phase is repeatedly washed with distilled water until no bromide ions remain. The organic phase is then transferred to a rotary evaporator and dichloromethane is removed by rotary evaporation at 60°C. The residue is then placed in a vacuum drying oven and dried under reduced pressure at 60°C for 3 hours to obtain EMITFSI ionic liquid.

[0111] Effect description: This comparative example abandons the microwave-assisted intermittent radiation mode of the example and adopts the traditional constant temperature water bath stirring process. The reaction time is greatly extended, the product purity is slightly lower than that of the example (uneven stirring and mixing, with a small amount of unreacted raw materials), and the energy consumption is higher.

[0112] Comparative Example 2: Synthesis of MOF-5 using conventional methods.

[0113] S1. Add 5 mmol of zinc acetate dihydrate and 5 mmol of terephthalic acid to a 100 mL conventional round-bottom flask, add 25 mL of DMF and 25 mL of ethanol, add 1 mL of triethylamine dropwise, and stir mechanically at room temperature for 30 min to initially disperse the materials.

[0114] S2, place the round-bottom flask in an oil bath, control the oil bath temperature at 90℃, and continue heating and refluxing for 8 hours.

[0115] S3. After the reaction is complete, the oil bath is turned off and the mixture is allowed to cool naturally to room temperature. It is then centrifuged at 3500 r / min for 10 min, and the precipitate is washed three times with DMF and ethanol respectively. It is then dried under vacuum at 65℃ for 6 h to obtain white powdered MOF-5.

[0116] Results: This comparative example abandons the microwave-assisted continuous radiation mode of the previous example and adopts the traditional oil bath heating reflux process, which greatly prolongs the reaction time. The resulting MOF-5 crystals are irregular, the specific surface area is lower than that of the previous example, the pore structure is partially collapsed, and the dispersibility is poor.

[0117] Comparative Example 3: Synthesis of EMITFSI@MOF-5 composite material by conventional method.

[0118] S1, weigh 1g of MOF-5 prepared in Comparative Example 2 and 2g of EMITFSI ionic liquid prepared in Comparative Example 1, add 10mL of ethylene glycol, place in a 100mL conventional beaker, and mechanically stir at room temperature for 3h.

[0119] S2. After stirring, the mixture is centrifuged at 7000 r / min for 10 min, the precipitate is collected, the precipitate is washed three times with acetone to remove residual solvent, and then vacuum dried at 80℃ for 2 h to obtain EMITFSI@MOF-5 composite material.

[0120] Effect description: This comparative example abandons the microwave-assisted intermittent radiation stirring mode of the embodiment and adopts the traditional room temperature mechanical stirring process. The ionic liquid can only adhere to the surface of MOF-5 and cannot effectively penetrate into the pores of MOF-5. The loading is lower than that of the embodiment and the loading uniformity is poor. Moreover, without microwave assistance, the interfacial bonding force between the ionic liquid and MOF-5 is weak and it is easy to fall off during subsequent use. The target performance of the composite material is significantly inferior to that of the embodiment.

[0121] Performance testing: XRD characterization: XRD test results are as follows Figure 1 As shown, in Figure 1 a. Imidazole-based ionic liquid@MOF-5 composite materials (BMITFSI@MOF-5, BMIFSI@MOF-5, EMITFSI@MOF-5, EMIFSI@MOF-5). EMIFSI@MOF-5 shows characteristic MOF-5 diffraction peaks at 2θ=5.2° and 9.6°, with sharp peaks and no impurities. The intensity is basically the same as that of pure MOF-5 and there is no shift. Figure 1 b. Pyrrolidine ionic liquid @MOF-5 composite material (PY 02 FSI@MOF-5, PY02 TFSI@MOF-5, PY 04 FSI@MOF-5, PY 04 TFSI@MOF-5, PY 14 FSI@MOF-5, PY 14 TFSI@MOF-5 also showed characteristic diffraction peaks at 2θ=5.2° and 9.6° that corresponded perfectly to pure MOF-5, with complete peak shapes and no obvious broadening or impurities. Figure 1 In the c-type ZIF-8 and MOF-5 based composite materials (BMIPF6@ZIF-8, EMIPF6@ZIF-8, BMIPF6@MOF-5, EMIPF6@MOF-5), BMIPF6@ZIF-8 exhibits characteristic diffraction peaks of ZIF-8 at 2θ=7.3° and 10.4°, while EMIPF6@MOF-5 exhibits characteristic diffraction peaks of MOF-5 at 2θ=5.2° and 9.6°. The peaks are sharp, free of impurities and shifted, and their intensity is basically consistent with that of the pure material.

[0122] The above results confirm that neither the loading process of imidazole-based nor pyrrolidine-based ionic liquids has damaged the crystal framework of MOF-5 or ZIF-8. Their structural integrity and crystallinity have been well preserved, indirectly indicating that the ionic liquids have been successfully encapsulated in the pores of the MOF material.

[0123] FTIR characterization: FTIR test results are as follows Figure 2 As shown, in Figure 2 In the imidazole ionic liquid@MOF-5 composite materials, EMIFSI@MOF-5, EMITFSI@MOF-5, BMIFSI@MOF-5, and BMITFSI@MOF-5 all retained the properties of pure MOF-5 at 3400 cm⁻¹. −1 Nearby hydroxyl stretching vibration peak, 1500 cm −1 Characteristic absorption peaks, such as those related to benzene ring skeletal vibrations, are also present in the 1100–1300 cm⁻¹ range. −1 The region exhibited ionic liquid anions (FSI). − TFSI − Characteristic vibration peaks; Figure 2 In the pyrrolidine ionic liquid@MOF-5 composite material (Figure 2b), PY 14 FSI@MOF-5, PY 14 The TFSI@MOF-5 sample also retained the characteristic absorption peaks of MOF-5, and these peaks were observed in the range of 1000–1400 cm⁻¹. −1 FSI appeared in the region − / TFSI − Characteristic peaks; Figure 2In the ZIF-8 based composite materials c, BMIPF6@ZIF-8 and EMIPF6@ZIF-8 retain the ZIF-8's properties at 1580 cm⁻¹. -1 Near the imidazole ring vibration peak, also at 830 cm⁻¹ −1 PF6 appeared nearby − The characteristic absorption peaks of MOF-5 are present, while EMIPF6@MOF-5 and BMIPF6@MOF-5 retain the characteristic peaks of MOF-5 and introduce the signal of PF6⁻.

[0124] The above results confirm that the characteristic functional groups of MOF-5 and ZIF-8 did not change significantly after ionic liquid loading. At the same time, the composite material showed the characteristic absorption peak of ionic liquid, indicating that the ionic liquid was successfully loaded onto the MOF material without destroying its framework functional group structure, which further corroborates the conclusions of XRD and SEM.

[0125] SEM characterization: Figure 3 SEM characterization results of MOF-5 and imidazole ionic liquid@MOF-5 and imidazole ionic liquid@ZIF-8 composites are shown. Among them, pure MOF-5 ( Figure 3 f) exhibits a fluffy, blocky morphology formed by irregular nanoparticle aggregation, with good particle size uniformity; BMIPF6@MOF-5 ( Figure 3 a) EMIPF6@MOF-5 ( Figure 3 c) and EMIFSI@MOF-5 ( Figure 3 e) The composite material retains similar particle aggregation characteristics to pure MOF-5, with only slight adhesion on the particle surface due to ionic liquid loading, and no significant change in particle size; while BMIPF6@ZIF-8 ( Figure 3 b) with EMIPF6@ZIF-8 ( Figure 3 d) exhibits a regular, spherical particle aggregation morphology with good particle dispersion, which is highly consistent with the typical morphological characteristics of ZIF-8.

[0126] DSC test: DSC test results are as follows Figure 4 As shown, in the imidazole system ( Figure 4 a) The pure ionic liquid EMITFSI exhibits obvious glass transition and melting endothermic peaks in the range of -86℃ to -49℃, and crystallization exothermic peaks in the range of 9℃ to 26℃, showing typical low-temperature phase transition behavior; while the loaded EMITFSI@MOF-5 composite material only shows a significantly weakened crystallization peak in the range of 27℃ to 32℃, the low-temperature characteristic phase transition peaks of the pure ionic liquid completely disappear, and compared with pure MOF-5 (which only shows a weak thermal effect in the range of 22℃ to 52℃), no additional abnormal thermal signals are observed.

[0127] In pyrrolidine systems ( Figure 4 b) Pure PY 14 TFSI also exhibits significant low-temperature endothermic peaks and intermediate-temperature crystallization peaks, while PY 14 The low-temperature phase transition peak of the TFSI@MOF-5 composite material disappeared, leaving only a weakened mid-temperature crystallization peak, indicating that the phase transition behavior of the ionic liquid was significantly suppressed.

[0128] In the ZIF-8 based composite system ( Figure 4 c) The characteristic thermal signal of pure ZIF-8 near -129.83℃ is completely preserved in EMIPF6@ZIF-8 and BMIPF6@ZIF-8. At the same time, the thermal effect peak shape of the composite material tends to be flat, and no characteristic phase transition signal of pure ionic liquid is observed. The thermal effect peak shape of MOF-5 based composite materials (BMIPF6@MOF-5, EMIPF6@MOF-5) is also significantly different from that of pure MOF-5, and it does not show the phase transition characteristics of pure ionic liquid.

[0129] Thermal stability test: The results of thermogravimetric analysis are as follows Figure 5 As shown, the decomposition temperature of the BMIPF6@ZIF-8 composite material is 565.3℃, and the decomposition temperature of the EMIFSI@MOF-5 composite material is 276.4℃, both of which are higher than those of the composite materials prepared without microwave method, and significantly better than those of pure ionic liquid. Microwave-assisted loading enhances the interaction between ionic liquid and MOF, effectively suppresses the volatilization of ionic liquid, and greatly improves thermal stability.

[0130] CO2 adsorption application test: 0.1 g of BMIPF6@ZIF-8 composite material was placed in 500 mL of industrial waste gas and CO2 was adsorbed at 25 °C and 1 atm. The adsorption capacity of BMIPF6@ZIF-8 composite material for CO2 in industrial waste gas was 3.6 mmol / g, which is much higher than that of pure ZIF-8 (CO2 adsorption capacity of 2.1 mmol / g) and composite materials prepared by traditional methods (CO2 adsorption capacity of 3.0 mmol / g), showing excellent selective adsorption performance. This is attributed to the uniform loading of ionic liquid and the good preservation of MOF porous structure after microwave optimization.

[0131] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A fluorine-containing ionic liquid@MOF composite material, characterized in that, The fluorine-containing ionic liquid@MOF composite material is obtained by mixing fluorine-containing ionic liquid and MOF in a solvent, and loading the ionic liquid onto the surface and pores of MOF by microwave-assisted loading method. The conditions for the microwave-assisted load method are: microwave power of 100W to 250W, temperature of 60℃ to 80℃, and microwave radiation time of 30min to 1h. The fluorinated ionic liquid is 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethylpyridinium bis(fluorosulfonyl)imide, 1-butylpyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(fluorosulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium hexafluorophosphate, or 1-butyl-3-methylimidazolium hexafluorophosphate.

2. The fluorine-containing ionic liquid@MOF composite material according to claim 1, characterized in that, The microwave is emitted intermittently, and the method of intermittent radiation is to irradiate for 8 minutes and then pause for 4 minutes.

3. The fluorine-containing ionic liquid@MOF composite material according to claim 1, characterized in that, The mass ratio of the fluorine-containing ionic liquid to the MOF is 0.5 to 3:

1.

4. The method for preparing the fluorine-containing ionic liquid@MOF composite material according to any one of claims 1 to 3, characterized in that, Includes the following steps: Using equimolar amounts of bromide salt and fluorinated sulfonyl imide lithium salt as raw materials, a metathesis reaction was carried out at 20℃~45℃ under the action of a first microwave to obtain a fluorinated ionic liquid. The fluorine-containing ionic liquid and MOF are mixed in a solvent, and the ionic liquid is loaded onto the surface and pores of the MOF under microwave radiation at 60℃~80℃ to obtain a fluorine-containing ionic liquid@MOF composite material.

5. The method for preparing the fluorine-containing ionic liquid@MOF composite material according to claim 4, characterized in that, The power of the first microwave is 100W to 300W, and the first microwave radiation lasts for 10 minutes with a 5-minute interval.

6. The method for preparing the fluorine-containing ionic liquid@MOF composite material according to claim 4, characterized in that, The preparation method of the MOF includes the following steps: mixing zinc acetate dihydrate with an organic ligand in an organic solvent and carrying out a coordination reaction under the action of a second microwave.

7. The method for preparing the fluorine-containing ionic liquid@MOF composite material according to claim 6, characterized in that, When the MOF is MOF-5, the power of the second microwave is 200W to 400W, the temperature is 80℃ to 100℃, and the reaction lasts for 1h to 2h. Alternatively, when the MOF is ZIF-8, the power of the second microwave is 150W to 350W, the temperature is 60℃ to 80℃, and the reaction lasts for 1h to 3h.

8. The method for preparing the fluorine-containing ionic liquid@MOF composite material according to claim 4, characterized in that, The solvent is ethylene glycol or dichloromethane.

9. The application of the fluorinated ionic liquid@MOF composite material according to any one of claims 1 to 3 as a CO2 adsorbent for capturing CO2 gas in industrial waste gas, characterized in that, The application includes the following steps: placing the fluorine-containing ionic liquid@MOF composite material in industrial waste gas and adsorbing CO2 gas in the industrial waste gas at 25°C and 1 atm.

10. The application of the fluorine-containing ionic liquid@MOF composite material according to claim 9 as a CO2 adsorbent for capturing CO2 gas in industrial waste gas, characterized in that, The ratio of the fluorine-containing ionic liquid@MOF composite material to industrial waste gas is 1g:5L~50L.

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