Highly hydrophobic MOF material for air purification of intelligent automobile cockpit and preparation method and application thereof

Abstract

The application relates to the technical field of gas adsorption materials, in particular to a high-hydrophobic MOF material for air purification of an intelligent automobile cabin and a preparation method and application thereof. The MOF material is prepared from 2,3,5,6-tetrafluoro-p-xylylene dimethyl ester as raw material through low-temperature nitration, sodium hydrosulfide nucleophilic substitution and in-situ protection treatment of acetic anhydride, and has 2,3,5,6-tetrafluoro-4-mercapto methyl benzoate with super-hydrophobic fluorine groups and high-activity mercapto groups; a solvent hot method modulated by hydrochloric acid is adopted to realize in-situ coordination crystallization of zirconium metal clusters and hybrid ligands, to complete the deprotection and activation of mercapto groups, and to prepare the MOF material with a stable zirconium cluster framework, a hydrophobic pore environment and specific adsorption sites. The MOF material of the application constructs a hydrophobic barrier through tetrafluoro groups to inhibit competitive adsorption of water molecules, utilizes mercapto groups to provide polar interaction and coordination sites to enhance the selective capture capacity of isopropyl alcohol, and significantly improves the adsorption efficiency and stability of the material in a humid environment.

Description

Technical Field

[0001] This invention relates to the field of gas adsorption materials technology, and in particular to highly hydrophobic MOF materials for air purification in automotive intelligent cabins, their preparation methods and applications. Background Technology

[0002] Isopropanol (IPA), a typical volatile organic solvent, is widely used in industries such as semiconductor cleaning, electronic device manufacturing, pharmaceutical synthesis, printing, and coatings. During these processes, large amounts of isopropanol vapor are released into the production environment or into the atmosphere.

[0003] Globally, environmental regulations targeting VOC emissions are becoming increasingly stringent, placing extremely high demands on the control of isopropanol concentration in cleanroom air for high-end manufacturing industries such as semiconductors. In photolithography, isopropanol gas molecules interact with photoresist, leading to linewidth distortion and pattern defects, especially in advanced processes like extreme ultraviolet (EUV) lithography, where this effect is more pronounced. Secondly, in microelectronic metallization processes, isopropanol undergoes a slow chemical reaction with noble metal interconnect layers (such as copper and aluminum), causing increased contact resistance and decreased circuit reliability over long-term exposure. Most importantly, in the presence of humidity, isopropanol can act as a carrier, promoting the transport and deposition of other contaminants, forming electrochemical corrosion microcells on device surfaces, and accelerating the corrosion process of metal wires.

[0004] Currently, mainstream AMC (Activated Molding Center) purification technologies mainly rely on multi-stage filtration systems, with adsorption materials playing a crucial role as the final protection layer. Activated carbon, as a traditional solution for mainstream final materials, boasts a high specific surface area of ​​over 1000 m² / g. However, its non-directional physical adsorption mechanism limits its selective capture capacity for polar isopropanol molecules. Furthermore, in high humidity environments, water molecules preferentially occupy its adsorption sites, leading to a sharp decline in its isopropanol adsorption performance. Chinese patent CN112107997A improves the affinity of activated carbon for oxygen-containing VOCs through surface oxidation modification, but the improvement in adsorption capacity and moisture resistance for isopropanol is still not significant, and there is a risk of secondary release due to non-specific desorption channels. High-silica zeolites (such as ZSM-5) are considered an alternative due to their hydrophobicity and regular microporous structure. They can achieve a certain degree of selective adsorption through pore size sieving. However, due to their limited pore size adjustment range and single adsorption force (mainly van der Waals forces), their capture strength for isopropanol is insufficient. They are prone to breakthrough when dealing with concentration fluctuations. For example, the zeolite composite material mentioned in patent CN108686629A generally has a low saturation adsorption capacity for trace isopropanol in dynamic adsorption tests. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a highly hydrophobic MOF material for air purification in automotive intelligent cockpits, its preparation method and application, so as to at least solve the problems of existing isopropanol adsorption materials having weak selective capture ability for isopropanol and low adsorption efficiency and stability in humid environments.

[0006] The present invention solves the above-mentioned technical problems through the following technical means:

[0007] In a first aspect, embodiments of the present invention provide a method for preparing highly hydrophobic MOF materials for air purification in automotive intelligent cockpits, the preparation method being as follows:

[0008] Using dimethyl 2,3,5,6-tetrafluoroterephthalate as a raw material, the mixture was subjected to low-temperature nitration, sodium hydrosulfide nucleophilic substitution, and in-situ protection with acetic anhydride to obtain methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

[0009] Zirconium tetrachloride, methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate, N,N-dimethylformamide, and concentrated hydrochloric acid were mixed, sealed, and reacted at 110–130 °C for 20–25 h. After natural cooling to room temperature, a reaction solution was obtained. The precipitate of the reaction solution was washed with N,N-dimethylformamide and then soaked in acetone several times. The resulting solid product was activated by heating for 10–15 h to obtain Zr-MOF material.

[0010] In some embodiments, the molar ratio of zirconium tetrachloride and methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate is 1:(1-2), the concentration of the concentrated hydrochloric acid is 37%, and 1 mmol of zirconium tetrachloride is suitable for 28-32 mL of concentrated hydrochloric acid.

[0011] In some embodiments, the precipitate is added to N,N-dimethylformamide, ultrasonically dispersed for 25–35 seconds, the supernatant is removed, and this step is repeated 3–5 times.

[0012] After washing, acetone is added to the precipitate, and the mixture is allowed to stand for 6-10 hours. The acetone is then removed, and this step is repeated 3-5 times to obtain a solid product.

[0013] In some embodiments, the solid product is activated by heating to 110–130°C for 12 hours.

[0014] In some embodiments, the methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate is prepared as follows:

[0015] (1) Take 2,3,5,6-tetrafluoro-4-nitrobenzene dimethyl ester and add concentrated sulfuric acid. After stirring and dissolving in an ice-water bath, add pre-cooled mixed acid dropwise. During the dropwise addition, control the temperature below 10℃. After the dropwise addition is complete, raise the temperature to room temperature and stir the reaction at room temperature for 10-14 hours. Pour the resulting reaction solution into crushed ice to precipitate crystals. Filter, wash with water until neutral, and dry under vacuum to obtain 2,3,5,6-tetrafluoro-4-nitrobenzene methyl ester.

[0016] (2) Methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate was added to N,N-dimethylformamide and stirred to dissolve under a nitrogen atmosphere. Sodium hydrosulfide hydrate was then added and heated to 38-45°C. The mixture was stirred for 3-5 hours. The resulting reaction product was cooled to room temperature and a mixture of acetic anhydride and anhydrous pyridine was added. The mixture was stirred for 2-4 hours at room temperature. The product was then poured into ice water and extracted with ethyl acetate. The product was washed once each with saturated sodium chloride solution, 1M hydrochloric acid, saturated sodium bicarbonate solution, and saturated sodium chloride solution. The resulting organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporator to obtain a pale yellow product. The product was purified by silica gel column chromatography to obtain methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate.

[0017] (3) Add methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate to a mixed solvent, stir to dissolve, add sodium hydroxide solution, heat to 65-75°C, stir and reflux for 5-7 hours, cool to room temperature, rotary evaporate the mixed solvent, acidify the remaining product with 6M dilute hydrochloric acid to pH=1.8-2.2, filter, wash with ice water, and vacuum dry to obtain methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

[0018] In some embodiments, in step (1), the concentration of concentrated sulfuric acid is 95% to 98%, the concentration of concentrated nitric acid is 69% to 72%, and the pre-cooled mixed acid is a mixture of concentrated nitric acid and 98% concentrated sulfuric acid in a volume ratio of 1:5. The mass-volume ratio of dimethyl 2,3,5,6-tetrafluoroterephthalate, concentrated sulfuric acid and pre-cooled mixed acid is 1g:(20 to 25)mL:2.4mL.

[0019] In some embodiments, in step (2), the mass content of the sodium hydrosulfide hydrate is 70%, and the mass-volume ratio of the methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate, sodium hydrosulfide hydrate, acetic anhydride and anhydrous pyridine is 1 g: (0.40-0.50) g: (1.5-2.0) mL: (1.2-1.3) mL.

[0020] In some embodiments, in step (3), the mixed solvent is a mixture of equal volumes of tetrahydrofuran and methanol, and the molar ratio of methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate to sodium hydroxide is 1:(12-15).

[0021] This invention discloses a method for preparing highly hydrophobic MOF materials. A three-step process—directional low-temperature nitration, aromatic nucleophilic substitution thiolation, and acetyl protection deprotection—is employed to prepare fluorinated thiol functional ligands, followed by in-situ construction of Zr-based MOF materials using a solvothermal method. The nitration reaction is conducted under strictly controlled low-temperature conditions, introducing a single nitro group at the 4-position of the benzene ring, eliminating multi-substitution byproducts. The strong electron-withdrawing effect of fluorine atoms is utilized throughout the process, ensuring specific reaction sites and significantly improving the purity of the target product while reducing the difficulty of separation and purification. Immediately after the thiol group is introduced via sodium hydrosulfide nucleophilic substitution, an acetic anhydride-pyridine system is used for acetyl protection, effectively preventing oxidation and polymerization of the active thiol group during reaction, post-processing, and storage. Subsequent alkaline and mild hydrolysis deprotection ensures that the mild conditions do not damage the fluorinated substitution structure of the benzene ring and the ester structure, resulting in a high-yield, high-purity functional 2,3,5,6-tetrafluoro-4-mercaptobenzoate. Ligand nitration employs a low-temperature controlled ice-water bath to avoid side reactions such as ester hydrolysis and fluorine atom loss under strong acid and high temperature. The entire process is free from extreme reaction conditions of high temperature and high pressure, ensuring safe experimental operation, low equipment requirements, and easy large-scale laboratory preparation. Using zirconium tetrachloride as the metal source and concentrated hydrochloric acid as the crystal form regulator, the hydrolysis rate of zirconium oxide clusters is effectively controlled, metal ion aggregation is inhibited, and the orderly coordination and self-assembly of organic ligands and inorganic metal clusters are promoted. After multiple washings with DMF, thorough exchange with acetone solvent, and vacuum heating activation, residual solvent and impurities in the pores are completely removed, resulting in Zr-MOF with complete crystal form, well-developed pores, and a stable framework structure.

[0022] Secondly, embodiments of the present invention provide a highly hydrophobic MOF material for air purification in automotive intelligent cockpits. The MOF material is prepared using the preparation method described in the first aspect, and the pore volume of the MOF material is 0.70–0.79 cm³. 3 / g.

[0023] The MOF material of the present invention has high hydrophobicity and also has a hydrophobic framework of perfluorobenzene ring, polar ester group and active thiol functional group. It has both hydrophobic and oleophilic properties, polar adsorption sites and active coordination sites. Compared with ordinary carboxylic acid Zr-MOF, it has significantly improved adsorption selectivity, molecular recognition ability and organic gas adsorption and separation performance, and has a wider range of applications.

[0024] Thirdly, embodiments of the present invention provide the application of the MOF material described in the second aspect in the preparation of isopropanol adsorbent materials.

[0025] Isopropanol molecules contain polar hydroxyl groups (-OH), which can form intermolecular hydrogen bonds with exposed carboxyl oxygen, coordinated water molecules, and oxygen-containing groups in the Zr-MOF framework, generating strong polar adsorption forces and enabling rapid capture of isopropanol molecules. The MOF material framework contains a high-density hydrophobic tetrafluorobenzene ring structure, and isopropanol has both hydrophobic alkyl chains and hydrophilic hydroxyl groups. The hydrophobic framework can form hydrophobic association with the alkyl segments of isopropanol, and combined with intermolecular van der Waals forces, it enhances the physical adsorption effect. The exposed thiol groups (-SH) on the surface of the MOF material are strong polar active sites, which can form weak polar interactions with the isopropanol hydroxyl groups, further enhancing the specific adsorption capacity for polar alcohol molecules. The activated MOF material has a regular hierarchical pore structure, and the pore size is highly matched with the dynamic size of isopropanol molecules. Relying on the physical spatial sieving effect, isopropanol molecules are confined and fixed inside the pores, realizing physical adsorption and storage. Attached Figure Description

[0026] Figure 1 This is a synthetic route diagram for MOF materials with high hydrophobicity;

[0027] Figure 2 This is the XRD pattern of the Zr-MOF material in Example 1;

[0028] Figure 3 These are nitrogen adsorption-desorption diagrams of the Zr-MOF materials in Examples 1-3;

[0029] Figure 4 This is a graph showing the contact angle test results of the Zr-MOF material in Example 1;

[0030] Figure 5 The images show the dynamic adsorption curves of isopropanol on the Zr-MOF materials in Examples 1-3.

[0031] Figure 6 This is a distribution diagram of the adsorption capacity of isopropanol for the Zr-MOF materials in Examples 1-3. Detailed Implementation

[0032] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0033] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0034] like Figure 1 As shown, this application provides a highly hydrophobic MOF material for air purification in automotive intelligent cockpits, its preparation method, and its application. This MOF material uses dimethyl 2,3,5,6-tetrafluoroterephthalate as a raw material and is synthesized via a multi-step route involving low-temperature nitration, sodium hydrosulfide nucleophilic substitution, and in-situ protection with acetic anhydride to prepare a hybrid ligand, methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate, possessing superhydrophobic fluorine groups and highly active thiol groups. A hydrochloric acid-modulated solvothermal method is used to achieve in-situ coordination crystallization of the zirconium metal cluster and the hybrid ligand, simultaneously completing the deprotection and activation of the thiol groups, ultimately yielding a Zr-MOF material with a stable zirconium cluster framework, a hydrophobic porous environment, and specific adsorption sites. This MOF material constructs a hydrophobic barrier through tetrafluoro groups to inhibit competitive adsorption of water molecules and utilizes thiol groups to provide polar interactions and coordination sites to enhance the selective capture ability of isopropanol, significantly improving the adsorption efficiency and stability of the material in humid environments.

[0035] Specifically, the preparation method of the highly hydrophobic MOF material for air purification in automotive intelligent cockpits in this application is as follows:

[0036] (1) Synthesis of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate

[0037] Weigh out dimethyl 2,3,5,6-tetrafluoro-4-nitrobenzene and add it to a round-bottom flask. Then add concentrated sulfuric acid (95-98%) and place the flask on a magnetic stirrer. Stir vigorously in an ice-water bath (0-5°C) until the solid is completely dissolved. Then slowly add a pre-cooled mixed acid consisting of concentrated nitric acid (69-72%) and concentrated sulfuric acid (98%), controlling the dropping rate. During the dropping process, keep the temperature of the reaction solution below 10°C. After the dropping is complete, remove the ice-water bath and allow the reaction solution to slowly rise to room temperature. Then continue stirring the reaction at room temperature for 10-14 hours. Pour the resulting reaction solution into crushed ice to precipitate crystals. Filter the solution and wash the solid with plenty of cold water until the filtrate is neutral. Transfer the solid to a watch glass and dry it in a vacuum drying oven at 50-55°C to obtain methyl 2,3,5,6-tetrafluoro-4-nitrobenzene.

[0038] In this step, the pre-cooled mixed acid is a mixture of concentrated nitric acid and 98% concentrated sulfuric acid with a volume ratio of 1:5. The mass-volume ratio of dimethyl 2,3,5,6-tetrafluoroterephthalate, concentrated sulfuric acid and pre-cooled mixed acid is 1g:(20-25)mL:2.4mL.

[0039] (2) Synthesis of methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate

[0040] Construct a three-necked round-bottom flask equipped with a magnetic stirrer, a reflux condenser, and a nitrogen delivery tube. Add methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate and anhydrous N,N-dimethylformamide to the three-necked round-bottom flask, turn on the nitrogen flow, and stir until the solids dissolve. Weigh out sodium hydrosulfide hydrate (NaSH·xH2O, mass content 70%) and quickly add it to the three-necked round-bottom flask under nitrogen protection. Heat the reaction system to 38–45°C and stir the reaction under nitrogen atmosphere for 3–5 hours. Monitor the reaction using TLC (developing solvent: petroleum ether / ethyl acetate = 4:1) until the substrate spots have essentially disappeared. The resulting reaction product was cooled to room temperature, and a mixture of acetic anhydride and anhydrous pyridine was slowly added to it through a constant-pressure dropping funnel. After the addition was complete, the mixture was stirred and protected at room temperature for 2–4 hours. The mixture was then poured into ice water and extracted with ethyl acetate (3 × 50 mL). The extract was then washed once each with saturated sodium chloride solution, 1M hydrochloric acid, saturated sodium bicarbonate solution, and saturated sodium chloride solution. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated using a rotary evaporator to obtain a pale yellow oil or solid. Purification was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, gradient from 10:1 to 5:1) to obtain a white solid, namely methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate.

[0041] In this step, the mass-to-volume ratio of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate, sodium hydrosulfide hydrate, acetic anhydride, and anhydrous pyridine is 1 g : (0.40–0.50) g ​​: (1.5–2.0) mL : (1.2–1.3) mL.

[0042] (3) Synthesis of ligand methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate

[0043] In a round-bottom flask, methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate was added, followed by an equal volume of tetrahydrofuran and methanol, and stirred to dissolve. Sodium hydroxide was dissolved in an aqueous solution to obtain a sodium hydroxide solution, which was then added to the round-bottom flask. A reflux condenser was installed, and the mixture was heated to 65–75°C and refluxed with stirring for 5–7 hours. After the reaction was complete, the mixture was cooled to room temperature, and most of the organic solvent was removed using a rotary evaporator. The remaining product was cooled in an ice-water bath and acidified to pH 1.8–2.2 with 6M dilute hydrochloric acid in a fume hood. A large amount of white solid should precipitate at this point. The solid was filtered and washed thoroughly with ice water 3–5 times. The solid was then placed in a vacuum drying oven and dried at 60°C for 12 hours to obtain a white powder, namely methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

[0044] In this step, the molar ratio of methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate to sodium hydroxide is 1:(12-15).

[0045] (4) Preparation of Zr-MOF

[0046] In a polytetrafluoroethylene (PTFE) liner, zirconium oxychloride (ZrCl4), methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate ligand, N,N-dimethylformamide, and concentrated hydrochloric acid (37%, as a modifier) ​​are added sequentially. The mixture is gently stirred with a glass rod for 30 seconds to ensure complete dispersion of all solids. The liner is then sealed in a stainless steel high-pressure reactor. The reactor is placed in an oven preheated to 110–130°C and reacted for 20–25 hours. After this, the oven heating is turned off, and the reactor is allowed to cool naturally to room temperature within the oven. Upon opening the reactor, a white or light yellow crystalline precipitate is observed on the lower part of the liner. The supernatant is carefully removed with a dropper, and fresh DMF is added. The mixture is then ultrasonically dispersed for 25–35 seconds, allowed to stand, and the supernatant is removed again. This process is repeated three times to wash away unreacted substances. Then acetone is added to soak the crystals, and the soaking is allowed to stand for 6-10 hours. The old acetone is removed, and this process is repeated 3-5 times, or until the crystals no longer dissolve significantly in acetone. The resulting solid product is heated to 110-130℃ and activated for 10-15 hours to obtain Zr-MOF material.

[0047] In this step, the molar ratio of zirconium tetrachloride to methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate is 1:(1-2), and 1 mmol of zirconium tetrachloride is suitable for 28-32 mL of concentrated hydrochloric acid.

[0048] The following examples 1-5 provide a detailed description of the highly hydrophobic MOF material and its preparation method of this application:

[0049] Example 1

[0050] The preparation method of the highly hydrophobic MOF material for air purification in automotive intelligent cockpits in this embodiment is as follows:

[0051] (1) Synthesis of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate

[0052] Weigh 1.00 g of dimethyl 2,3,5,6-tetrafluoro-4-nitrobenzene and add it to a round-bottom flask. Then add 20 mL of concentrated sulfuric acid (98%) and place the flask on a magnetic stirrer. Stir vigorously in an ice-water bath (0-5°C) until the solid is completely dissolved. Then slowly add a pre-cooled mixed acid consisting of 0.40 mL of concentrated nitric acid (69%) and 2 mL of concentrated sulfuric acid (98%), controlling the dropping rate. During the dropping process, keep the temperature of the reaction solution below 10°C. After the dropping is completed in 30 min, remove the ice-water bath and allow the reaction solution to slowly rise to room temperature. Then continue stirring at room temperature for 12 h. Pour the resulting reaction solution into crushed ice to precipitate crystals. Filter the solution and wash the solid with plenty of cold water until the filtrate is neutral. Transfer the solid to a watch glass and dry it in a vacuum drying oven at 50°C to obtain methyl 2,3,5,6-tetrafluoro-4-nitrobenzene.

[0053] (2) Synthesis of methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate

[0054] Construct a three-necked round-bottom flask equipped with a magnetic stirrer, a reflux condenser, and a nitrogen delivery tube. Add 0.8 g of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate and 30 mL of anhydrous N,N-dimethylformamide to the three-necked round-bottom flask. Turn on the nitrogen flow and stir until the solid dissolves. Weigh 0.32 g of sodium hydrosulfide hydrate (NaSH·xH2O, 70% by mass) and quickly add it to the three-necked round-bottom flask under nitrogen protection. Heat the reaction system to 40 °C and stir under nitrogen atmosphere for 4 h. Monitor the reaction using TLC (electrolyte: petroleum ether / ethyl acetate = 4:1) until the substrate spots have essentially disappeared. The resulting reaction product was cooled to room temperature, and a mixture of 1.2 mL of acetic anhydride and 1.0 mL of anhydrous pyridine was slowly added to it through a constant-pressure dropping funnel. After the addition was complete, the mixture was stirred and protected at room temperature for 3 hours. The mixture was then poured into 150 mL of ice water and extracted with ethyl acetate (3 × 50 mL). The extract was then washed once each with 50 mL of saturated sodium chloride solution, 50 mL of 1M hydrochloric acid, 50 mL of saturated sodium bicarbonate solution, and saturated sodium chloride solution. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated using a rotary evaporator to obtain a pale yellow oil or solid. Purification was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, gradient from 10:1 to 5:1) to obtain a white solid, namely methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate.

[0055] (3) Synthesis of ligand methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate

[0056] In a round-bottom flask, add 0.7 g of methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate, followed by a mixed solvent of 15 mL tetrahydrofuran and 15 mL methanol, and stir to dissolve. Dissolve 1.53 g of sodium hydroxide in 15 mL of aqueous solution to obtain a sodium hydroxide solution. Add the sodium hydroxide solution to the round-bottom flask, install a reflux condenser, heat to 70 °C, and stir under reflux for 6 h. After the reaction is complete, cool to room temperature and remove most of the organic solvent using a rotary evaporator. Cool the remaining product in an ice-water bath and acidify to pH 2.0 with 6 M dilute hydrochloric acid in a fume hood. At this point, a large amount of white solid should precipitate. Filter the solid and wash it thoroughly with ice water four times. Place the solid in a vacuum drying oven and dry at 60 °C for 12 h to obtain a white powder, namely methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

[0057] (4) Preparation of Zr-MOF

[0058] In a polytetrafluoroethylene (PTFE) liner, 233 mg of zirconium oxychloride (ZrCl4), 270 mg of methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate ligand, 10 mL of N,N-dimethylformamide, and 30 mL of concentrated hydrochloric acid (37%, as a modifier) ​​were added sequentially. The mixture was gently stirred with a glass rod for 30 seconds to ensure thorough dispersion of all solids. The liner was sealed in a stainless steel high-pressure reactor, which was then placed in an oven preheated to 120°C. After reacting for 24 hours, the oven heating was turned off, and the reactor was allowed to cool naturally to room temperature inside the oven. Upon opening the reactor, a white or light yellow crystalline precipitate was observed on the lower part of the liner. The supernatant was carefully removed with a dropper, and then 10 mL of fresh DMF was added. The mixture was ultrasonically dispersed for 30 seconds, allowed to stand, and the supernatant was removed again. This process was repeated three times to wash away unreacted substances. Acetone was then added to soak the crystals, which were left to stand for 8 hours. The old acetone was removed, and this process was repeated 4 times, or until the crystals no longer showed significant dissolution in acetone. The resulting solid product was heated to 120°C and activated for 12 hours to obtain the Zr-MOF material, denoted as MOF-1.

[0059] Example 2

[0060] Replace “270mg methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate” in step (2) of Example 1 with “400mg methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate”, while keeping other conditions unchanged, to obtain the target material, denoted as MOF-2.

[0061] Example 3

[0062] Replace “270mg methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate” in step (2) of Example 1 with “540mg methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate”, while keeping other conditions unchanged, to obtain the target material, denoted as MOF-3.

[0063] Example 4

[0064] The preparation method of the highly hydrophobic MOF material for air purification in automotive intelligent cockpits in this embodiment is as follows:

[0065] (1) Synthesis of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate

[0066] Weigh 1 g of dimethyl 2,3,5,6-tetrafluoro-4-nitrobenzene and add it to a round-bottom flask. Then add 22 mL of concentrated sulfuric acid (95%) and place the flask on a magnetic stirrer. Stir vigorously in an ice-water bath (0-5°C) until the solid is completely dissolved. Then slowly add a pre-cooled mixed acid consisting of 0.4 mL of concentrated nitric acid (72%) and 2 mL of concentrated sulfuric acid (98%), controlling the dropping rate. During the dropping process, keep the temperature of the reaction solution below 10°C. After the dropping is complete, remove the ice-water bath and allow the reaction solution to slowly rise to room temperature. Then continue stirring at room temperature for 10 h. Pour the resulting reaction solution into crushed ice to precipitate crystals. Filter the solution and wash the solid with plenty of cold water until the filtrate is neutral. Transfer the solid to a watch glass and dry it in a vacuum drying oven at 53°C to obtain methyl 2,3,5,6-tetrafluoro-4-nitrobenzene.

[0067] (2) Synthesis of methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate

[0068] Set up a three-necked round-bottom flask equipped with a magnetic stirrer, a reflux condenser, and a nitrogen delivery tube. Add 1 g of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate and 35 mL of anhydrous N,N-dimethylformamide to the three-necked round-bottom flask. Turn on the nitrogen flow and stir until the solid dissolves. Weigh 0.45 g of sodium hydrosulfide hydrate (NaSH·xH2O, mass content 70%) and quickly add it to the three-necked round-bottom flask under nitrogen protection. Heat the reaction system to 38 °C and stir under nitrogen atmosphere for 3 h. Monitor the reaction using TLC (electrolyte: petroleum ether / ethyl acetate = 4:1) until the substrate spots have basically disappeared. The resulting reaction product was cooled to room temperature, and a mixture of 1.8 mL of acetic anhydride and 1.2 mL of anhydrous pyridine was slowly added to it through a constant-pressure dropping funnel. After the addition was complete, the mixture was stirred and protected at room temperature for 2 hours. The mixture was then poured into ice water and extracted with ethyl acetate (3 × 50 mL). The extract was then washed once each with saturated sodium chloride solution, 1 M hydrochloric acid, saturated sodium bicarbonate solution, and saturated sodium chloride solution. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated using a rotary evaporator to obtain a pale yellow oil or solid. Purification was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, gradient from 10:1 to 5:1) to obtain a white solid, namely methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate.

[0069] (3) Synthesis of ligand methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate

[0070] In a round-bottom flask, add 0.7 g of methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate, followed by a mixture of 15 mL tetrahydrofuran and 15 mL methanol, and stir to dissolve. Dissolve 1.32 g of sodium hydroxide in 15 mL of aqueous solution to obtain a sodium hydroxide solution. Add the sodium hydroxide solution to the round-bottom flask, install a reflux condenser, and heat to 65 °C. Reflux the mixture with stirring for 5 h. After the reaction is complete, cool to room temperature and remove most of the organic solvent using a rotary evaporator. Cool the remaining product in an ice-water bath and acidify it to pH 1.8 with 6 M dilute hydrochloric acid in a fume hood. At this point, a large amount of white solid should precipitate. Filter the solid and wash it thoroughly three times with ice water. Place the solid in a vacuum drying oven and dry at 60 °C for 12 h to obtain a white powder, namely methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

[0071] (4) Preparation of Zr-MOF

[0072] In a polytetrafluoroethylene (PTFE) liner, 233 mg of zirconium oxychloride (ZrCl4), 400 mg of methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate ligand, 10 mL of N,N-dimethylformamide, and 28 mL of concentrated hydrochloric acid (37%, as a modifier) ​​were added sequentially. The mixture was gently stirred with a glass rod for 30 seconds to ensure thorough dispersion of all solids. The liner was sealed in a stainless steel high-pressure reactor, which was then placed in an oven preheated to 110°C. After reacting for 20 hours, the oven heating was turned off, and the reactor was allowed to cool naturally to room temperature inside the oven. Upon opening the reactor, a white or light yellow crystalline precipitate was observed on the lower part of the liner. The supernatant was carefully removed with a dropper, and then fresh DMF was added. The mixture was ultrasonically dispersed for 25 seconds, allowed to stand, and the supernatant was removed again. This process was repeated three times to wash away unreacted substances. Acetone was then added to soak the crystals, which were left to stand for 6 hours. The old acetone was removed, and this process was repeated 3 times, or until the crystals no longer showed significant dissolution in acetone. The resulting solid product was then heated to 110°C and activated for 10 hours to obtain Zr-MOF material.

[0073] Example 5

[0074] The preparation method of the highly hydrophobic MOF material for air purification in automotive intelligent cockpits in this embodiment is as follows:

[0075] (1) Synthesis of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate

[0076] Weigh 1.00 g of dimethyl 2,3,5,6-tetrafluoro-4-nitrobenzene and add it to a round-bottom flask. Then add 25 mL of concentrated sulfuric acid (96%) and place the flask on a magnetic stirrer. Stir vigorously in an ice-water bath (0-5°C) until the solid is completely dissolved. Then slowly add a pre-cooled mixed acid consisting of 0.40 mL of concentrated nitric acid (72%) and 2 mL of concentrated sulfuric acid (98%), controlling the dropping rate. During the dropping process, keep the temperature of the reaction solution below 10°C. After the dropping is complete, remove the ice-water bath and allow the reaction solution to slowly rise to room temperature. Then continue stirring the reaction at room temperature for 14 h. Pour the resulting reaction solution into crushed ice to precipitate crystals. Filter the solution and wash the solid with plenty of cold water until the filtrate is neutral. Transfer the solid to a watch glass and dry it in a vacuum drying oven at 55°C to obtain methyl 2,3,5,6-tetrafluoro-4-nitrobenzene.

[0077] (2) Synthesis of methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate

[0078] Set up a three-necked round-bottom flask equipped with a magnetic stirrer, a reflux condenser, and a nitrogen delivery tube. Add 1 g of methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate and 35 mL of anhydrous N,N-dimethylformamide to the three-necked round-bottom flask. Turn on the nitrogen flow and stir until the solid dissolves. Weigh 2.0 g of sodium hydrosulfide hydrate (NaSH·xH2O, mass content 70%) and quickly add it to the three-necked round-bottom flask under nitrogen protection. Heat the reaction system to 45 °C and stir under nitrogen atmosphere for 5 h. Monitor the reaction using TLC (electrolyte: petroleum ether / ethyl acetate = 4:1) until the substrate spots have basically disappeared. The resulting reaction product was cooled to room temperature, and a mixture of 2.0 mL of acetic anhydride and 1.3 mL of anhydrous pyridine was slowly added to it through a constant-pressure dropping funnel. After the addition was complete, the mixture was stirred and protected for 4 hours at room temperature. The mixture was then poured into ice water and extracted with ethyl acetate (3 × 50 mL). The extract was then washed once each with saturated sodium chloride solution, 1 M hydrochloric acid, saturated sodium bicarbonate solution, and saturated sodium chloride solution. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated using a rotary evaporator to obtain a pale yellow oil or solid. Purification was performed by silica gel column chromatography (eluent: petroleum ether / ethyl acetate, gradient from 10:1 to 5:1) to obtain a white solid, namely methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate.

[0079] (3) Synthesis of ligand methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate

[0080] In a round-bottom flask, add 0.7 g of methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate, followed by a mixture of 15 mL tetrahydrofuran and 15 mL methanol, and stir to dissolve. Dissolve 1.65 g of sodium hydroxide in 20 mL of aqueous solution to obtain a sodium hydroxide solution. Add the sodium hydroxide solution to the round-bottom flask, install a reflux condenser, heat to 75 °C, and stir under reflux for 7 h. After the reaction is complete, cool to room temperature and remove most of the organic solvent using a rotary evaporator. Cool the remaining product in an ice-water bath and acidify to pH 2.2 with 6 M dilute hydrochloric acid in a fume hood. At this point, a large amount of white solid should precipitate. Filter the solid and wash it thoroughly with ice water five times. Place the solid in a vacuum drying oven and dry at 60 °C for 12 h to obtain a white powder, namely methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

[0081] (4) Preparation of Zr-MOF

[0082] In a polytetrafluoroethylene (PTFE) liner, 233 mg of zirconium oxychloride (ZrCl4), 400 mg of methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate ligand, 10 mL of N,N-dimethylformamide, and 32 mL of concentrated hydrochloric acid (37%, as a modifier) ​​were added sequentially. The mixture was gently stirred with a glass rod for 35 seconds to ensure thorough dispersion of all solids. The liner was sealed in a stainless steel high-pressure reactor, which was then placed in an oven preheated to 130°C. After reacting for 25 hours, the oven heating was turned off, and the reactor was allowed to cool naturally to room temperature inside the oven. Upon opening the reactor, a white or light yellow crystalline precipitate was observed on the lower part of the liner. The supernatant was carefully removed with a dropper, and then fresh DMF was added. The mixture was ultrasonically dispersed for 35 seconds, allowed to stand, and the supernatant was removed again. This process was repeated three times to wash away unreacted substances. Acetone was then added to soak the crystals, which were left to stand for 10 hours. The old acetone was then removed, and this process was repeated 5 times, or until the crystals no longer showed significant dissolution in acetone. The resulting solid product was then heated to 130°C and activated for 15 hours to obtain the Zr-MOF material.

[0083] Structural characterization and performance testing:

[0084] (1) XRD characterization

[0085] Using the Zr-MOF material from Example 1 as a sample, an X-ray diffractometer (Bruker D8 Advance, Germany) was used. The scanning range was set to 5-50°, the scanning speed to 10° / min, and the step size to 0.05°. The diffraction pattern was analyzed to obtain information such as phase composition and crystallinity. The XRD pattern of the Zr-MOF material from Example 1 is shown below. Figure 2 As shown.

[0086] from Figure 2 It can be seen that the baseline is stable and there are no obvious bulges (weak amorphous background), indicating that the MOF-1 material has high crystallinity and few amorphous impurities. All diffraction peaks are sharp, symmetrical and narrow, indicating that the MOF-1 has a large grain size and regular crystal structure.

[0087] (2) Specific surface area and pore size test analysis

[0088] Using the Zr-MOF materials from Examples 1-3 as samples, the BET surface area and pore structure of the materials were tested at -195°C using a Belserp MAX II analyzer with N2 adsorption and desorption. The total surface area was determined using the Brunol-Emmett-Taylor (BET) equation. The results are shown in Table 1 and... Figure 3 As shown.

[0089] Table 1

[0090] Example 1 1415 0.70 Example 2 1445 0.75 Example 3 1508 0.79

[0091] Figure 3 The data in Table 1 show that with excessive ligands (Examples 2 and 3), the pore volume and specific surface area of ​​the material decreased. This may be because the excess ligands occupied some coordination sites during the synthesis process, leading to an increase in framework defects or blocking some pores, ultimately affecting the porous properties of the material. Overall, the Zr-MOF material of this invention has high specific surface area and pore volume, is a typical microporous material, and has good physical adsorption potential for small molecules (such as isopropanol).

[0092] (3) Contact angle test

[0093] Using the Zr-MOF material from Example 1 as a sample, the water contact angle of the material was measured using a contact angle meter (Esr-N, Germany) to determine the sample's affinity for water. The solid sample was pressed into a thin sheet using a tablet press, and the liquid was evenly coated onto a glass slide, which was then placed on the sample stage, and the stage was adjusted to a suitable height. The hydrophobicity of the material surface can be categorized as hydrophilic (CA < 90º) and hydrophobic (CA > 90º); the larger the contact angle, the stronger the hydrophobicity. The test results are as follows: Figure 4 As shown.

[0094] from Figure 4 As can be seen, the contact angle of the MOF-based gas adsorbent prepared in Example 1 is 125.6°, which is much greater than 90°. This indicates that the prepared MOF material surface has clear and stable hydrophobic properties, ensuring the structural integrity and stability of the MOF material under humid conditions. More importantly, the hydrophobic surface can reduce the competitive adsorption of water molecules and isopropanol molecules at the adsorption sites, thereby improving the adsorption selectivity and adsorption kinetic efficiency of the MOF material for isopropanol.

[0095] (4) Dynamic adsorption test

[0096] Using the Zr-MOF materials from Examples 1-3 as samples, isopropanol adsorption tests were conducted on the materials using a UTEST static adsorption apparatus. Initial efficiency: test airflow (12 L / min), test resistance (100 Pa), and test concentration (600 ppb) were controlled; dirt holding capacity: test airflow (15 L / min), test resistance (100 Pa), and test concentration (10 ppm) were controlled. The adsorption capacity was calculated using the integral of the breakthrough curve, as shown in the following formula:

[0097]

[0098] In the formula, q (g / g) is the maximum adsorption capacity, F (mL / min) is the total gas flow rate, and C0 and C (mg / m³) are also present. 3 The inlet and outlet concentrations of isopropanol are denoted as m(g) and t(t), respectively. s (min) represents the adsorption time.

[0099] The dynamic adsorption curves of isopropanol for the Zr-MOF materials in Examples 1-3 are as follows: Figure 5 As shown, the adsorption capacity distribution of isopropanol for the Zr-MOF materials in Examples 1-3 is as follows. Figure 6 As shown. Figure 5 The isopropanol breakthrough curves showed that the Zr-MOF in Example 1 reached adsorption saturation first (C / CO rapidly increased to 1.0), while Example 3 had the longest breakthrough time, indicating that as the ligand feed ratio increased, the adsorption kinetics of the material for isopropanol slowed down and the mass transfer resistance increased; combined with Figure 6 The cumulative adsorption capacity histogram shows that Example 3 had the highest adsorption capacity (108 mg / g), followed by Example 2 (100 mg / g), and Example 1 had the lowest (93 mg / g). This indicates that although excess ligand leads to a decrease in pore volume, the introduced additional thiol sites enhance the polar interaction with isopropanol, ultimately increasing the saturated adsorption capacity. This demonstrates the synergistic regulation of adsorption performance by ligand functional group effects and pore structure. Figure 5 and Figure 6 It can be seen that the MOF material of the present invention exhibits high adsorption performance for isopropanol.

[0100] Therefore, the MOF material of the present invention can be used to prepare isopropanol adsorbent materials.

[0101] The foregoing description includes examples from this specification. Of course, for the purposes of describing this specification, it is impossible to describe every conceivable combination of components or methods; however, those skilled in the art will understand that many other combinations and arrangements are possible. Therefore, this specification is intended to cover all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, with regard to the use of the term "comprising" in the detailed description or claims, the term is intended to be inclusive in a manner similar to the term "including," as interpreted when "comprising" is used as a transitional word in the claims.

[0102] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing highly hydrophobic MOF materials for air purification in automotive intelligent cockpits, characterized in that, The preparation method is as follows: Using dimethyl 2,3,5,6-tetrafluoroterephthalate as a raw material, the mixture was subjected to low-temperature nitration, sodium hydrosulfide nucleophilic substitution, and in-situ protection with acetic anhydride to obtain methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate. Zirconium tetrachloride, methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate, N,N-dimethylformamide, and concentrated hydrochloric acid were mixed, sealed, and reacted at 110–130 °C for 20–25 h. After natural cooling to room temperature, a reaction solution was obtained. The precipitate of the reaction solution was washed with N,N-dimethylformamide and then soaked in acetone several times. The resulting solid product was activated by heating for 10–15 h to obtain Zr-MOF material.

2. The preparation method according to claim 1, characterized in that, The molar ratio of zirconium tetrachloride to methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate is 1:(1-2), the concentration of the concentrated hydrochloric acid is 37%, and 1 mmol of zirconium tetrachloride is suitable for 28-32 mL of concentrated hydrochloric acid.

3. The preparation method according to claim 1, characterized in that, The precipitate was added to N,N-dimethylformamide, ultrasonically dispersed for 25-35 seconds, and the supernatant was removed. This step was repeated 3-5 times. After washing, acetone is added to the precipitate and the mixture is allowed to stand for 6–10 hours. The acetone is then removed, and this step is repeated 3–5 times to obtain a solid product.

4. The preparation method according to claim 1, characterized in that, The solid product is activated by heating to 110–130°C for 12 hours.

5. The preparation method according to claim 1, characterized in that, The preparation method of the methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate is as follows: (1) Take 2,3,5,6-tetrafluoro-4-nitrobenzene dimethyl ester and add concentrated sulfuric acid. After stirring and dissolving in an ice-water bath, add pre-cooled mixed acid dropwise. During the dropwise addition, control the temperature below 10℃. After the dropwise addition is complete, raise the temperature to room temperature and stir the reaction at room temperature for 10-14 hours. Pour the resulting reaction solution into crushed ice to precipitate crystals. Filter, wash with water until neutral, and dry under vacuum to obtain 2,3,5,6-tetrafluoro-4-nitrobenzene methyl ester. (2) Methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate was added to N,N-dimethylformamide and stirred to dissolve under a nitrogen atmosphere. Sodium hydrosulfide hydrate was then added and heated to 38-45°C. The mixture was stirred for 3-5 hours. The resulting reaction product was cooled to room temperature and a mixture of acetic anhydride and anhydrous pyridine was added. The mixture was stirred for 2-4 hours at room temperature. The product was then poured into ice water and extracted with ethyl acetate. The product was washed once each with saturated sodium chloride solution, 1M hydrochloric acid, saturated sodium bicarbonate solution, and saturated sodium chloride solution. The resulting organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporator to obtain a pale yellow product. The product was purified by silica gel column chromatography to obtain methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate. (3) Add methyl 2,3,5,6-tetrafluoro-4-acetylmercaptobenzoate to a mixed solvent, stir to dissolve, add sodium hydroxide solution, heat to 65-75°C, stir and reflux for 5-7 hours, cool to room temperature, rotary evaporate the mixed solvent, acidify the remaining product with 6M dilute hydrochloric acid to pH=1.8-2.2, filter, wash with ice water, and vacuum dry to obtain methyl 2,3,5,6-tetrafluoro-4-mercaptobenzoate.

6. The preparation method according to claim 5, characterized in that, In step (1), the concentration of concentrated sulfuric acid is 95%–98%, the concentration of concentrated nitric acid is 69%–72%, and the pre-cooled mixed acid is a mixture of concentrated nitric acid and 98% concentrated sulfuric acid with a volume ratio of 1:

5. The mass-volume ratio of dimethyl 2,3,5,6-tetrafluoroterephthalate, concentrated sulfuric acid, and pre-cooled mixed acid is 1g:(20–25)mL:2.4mL.

7. The preparation method according to claim 5, characterized in that, In step (2), the mass content of the sodium hydrosulfide hydrate is 70%, and the mass-volume ratio of the methyl 2,3,5,6-tetrafluoro-4-nitrobenzoate, sodium hydrosulfide hydrate, acetic anhydride and anhydrous pyridine is 1 g: (0.40-0.50) g: (1.5-2.0) mL: (1.2-1.3) mL.

8. The preparation method according to claim 5, characterized in that, In step (3), the mixed solvent is a mixture of equal volumes of tetrahydrofuran and methanol, and the molar ratio of methyl 2,3,5,6-tetrafluoro-4-acetyl mercaptobenzoate to sodium hydroxide is 1:(12-15).

9. A highly hydrophobic MOF material for air purification in automotive intelligent cockpits, characterized in that, The MOF material is prepared using the preparation method described in any one of claims 1-8, and the pore volume of the MOF material is 0.70–0.79 cm³. 3 / g.

10. The application of the MOF material according to claim 9 in the preparation of isopropanol adsorbent materials.

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