Super-hydrophobic MOF-UiO-67-F4 / MS material as well as preparation method and application thereof

Abstract

The invention discloses a super-hydrophobic MOF-UiO-67-F4 / MS material as well as a preparation method and application thereof, and belongs to the technical field of materials. A fluorine-containing functional group compound and a carboxyl-containing functional group compound are used as ligands, zirconium chloride is used as a metal source, N, N-dimethylformamide is used as a solvent, benzoic acid is used as a morphology regulator, and the super-hydrophobic MOF-UiO-67-F4 / MS material is prepared by adopting a solvothermal method. The material has a hierarchical pore structure and contains a hydrophobic functional group fluorine atoms, compared with MOF-UiO-67 / MS and MOF-UiO-66-F4 / MS materials, the adsorption capacity of MOF-UiO-67-F4 / MS to environmental organic pollutants is greatly improved, and the adsorption performance is 1.08-1.32 times that of the MOF-UiO-67 / MS material and 1.12-1.55 times that of the MOF-UiO-66-F4 / MS material. The preparation method disclosed by the invention is simple in preparation process, and the obtained super-hydrophobic MOF-UiO-67-F4 / MS material has super-good adsorption capacity on environmental organic pollutants.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and in particular relates to a super-hydrophobic MOF-UiO-67-F4 / MS material and a preparation method and application thereof. Background Art

[0002] With the frequent illegal discharge of industrial oily wastewater and marine oil spills, oil pollution has become a global environmental governance problem. The mainstream oil-water separation methods currently include in-situ incineration, chemical dispersion, and biodegradation. Among them, although the in-situ incineration method can quickly remove the oil film, it will produce toxic and harmful gases, thereby causing secondary pollution; the chemical dispersion method requires the use of chemical dispersants, which may increase the toxicity of the water body; and the biodegradation method has problems such as long operation cycle, low degradation efficiency, and high cost. Among them, the adsorption method is widely used due to its advantages such as high cost-effectiveness, easy operation and high efficiency. Sponge is considered to be an ideal oil absorption material due to its low cost, large pore structure, and strong oil absorption capacity. Melamine sponge (MS) is a new type of foam plastic with a three-dimensional grid structure with a high open porosity. It has attracted widespread attention due to its advantages such as high elasticity and porosity, easy recycling, and stable mechanical properties. However, melamine sponge (MS) is hydrophilic and lacks oil / water selectivity. Therefore, it needs to be hydrophobic before being used as an oil absorption material.

[0003] Metal-organic frameworks (MOFs) are a type of crystalline porous material with a periodic network structure formed by the self-assembly of inorganic metal centers (metal ions or metal clusters) and bridging organic ligands. They have shown their competitiveness in improving the hydrophobicity of sponges. MOF materials can not only increase the roughness of the sponge skeleton, but also reduce its surface free energy, which makes it possible to obtain super-hydrophobic and super-oleophilic sponges. However, the existing methods for synthesizing MOF / MS with good oil-water separation effect and good performance in adsorbing environmental organic pollutants are mostly complicated. How to effectively and simply prepare MOF / MS with good oil-water separation effect and good performance in adsorbing environmental organic pollutants is still a challenge. Summary of the invention

[0004] In view of the above technical problems, the present invention proposes a super hydrophobic MOF-UiO-67-F4 / MS material and its preparation method and application. The MOF-UiO-67-F4 of the present invention is self-assembled from tetrafluoroterephthalic acid ligands containing fluorine functional groups, zirconium tetrachloride ligands containing chlorine functional groups and 4,4'-biphenyldicarboxylic acid ligands containing carboxyl groups. MOF-UiO-67-F4 / MS can efficiently adsorb organic pollutants in the environment, showing excellent reproducibility and reusability, and its preparation process is simple, low cost, and has good application prospects.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the purposes of the present invention is to provide a super-hydrophobic MOF-UiO-67-F4 / MS material, which is prepared by a solvothermal method using a fluorine-containing functional group compound and a carboxyl-containing functional group compound as ligands, zirconium tetrachloride as a metal source, N,N-dimethylformamide (DMF) as a solvent, and benzoic acid as a morphology regulator; wherein the fluorine-containing functional group compound is tetrafluoroterephthalic acid, and the carboxyl-containing functional group compound is 4,4'-biphenyldicarboxylic acid.

[0007] The MOF-UiO-67-F4 of the present invention is assembled from a tetrafluoroterephthalic acid ligand containing a fluorine functional group, a 4,4'-biphenyl dicarboxylic acid ligand containing a carboxyl group, and a zirconium tetrachloride metal source, wherein the tetrafluoroterephthalic acid ligand contains four fluorine functional groups and two carboxyl functional groups, the 4,4'-biphenyl dicarboxylic acid ligand contains two carboxyl functional groups, and the zirconium tetrachloride ligand contains a coordinated zirconium metal ion. The presence of fluorine atoms significantly enhances the hydrophobicity of the material, so that it exhibits better selectivity and adsorption performance in oil-water separation and organic pollutant adsorption. The hydrophobic functional group can effectively reduce the surface free energy of the material, thereby increasing the affinity for oils and organic pollutants. The 4,4'-biphenyl dicarboxylic acid ligand containing a carboxyl functional group not only participates in the construction of the MOF, but also provides additional adsorption sites. The carboxyl group can interact with the organic pollutant molecules through hydrogen bonds or electrostatic interactions, further enhancing the adsorption capacity. Benzoic acid, as a morphology regulator, can effectively regulate the crystal morphology and pore structure of MOF. The optimized morphology and pore structure help to improve the adsorption performance of the material, making it more suitable for oil-water separation and organic pollutant adsorption. In the process of synthesizing MOF-UiO-67-F4, DMF was used as a solvent and benzoic acid was used as a morphology regulator. It was prepared by a solvothermal method at 100°C; and compared with other methods for preparing MOF metal organic frameworks, this method uses a one-step bonding method, and the operation process is simple and the process is simple. The prepared MOF-UiO-67-F4 / MS material has a multi-level pore structure, which can provide more adsorption sites and a larger specific surface area, thereby significantly improving the adsorption capacity of organic pollutants. The multi-level pore structure not only increases the number of adsorption sites, but also improves the mass transfer efficiency of the material, making it easier for pollutant molecules to enter the material for adsorption.

[0008] Further, the concentration of tetrafluoroterephthalic acid in the solvent is 0.01-0.03M; the concentration of 4,4'-biphenyldicarboxylic acid in the solvent is 0.01-0.03M; the concentration of zirconium tetrachloride in the solvent is 0.0068-0.02M, that is, the molar ratio of zirconium tetrachloride to the ligand is 1:3.

[0009] Furthermore, the molar ratio of the benzoic acid to the zirconium chloride is 1:1.

[0010] The second object of the present invention is to provide a method for preparing a super hydrophobic MOF-UiO-67-F4 / MS material, comprising the following steps:

[0011] Dopamine hydrochloride was dispersed in Tris buffer, and a cleaned melamine sponge (MS) was immersed therein and allowed to stand, and then the obtained sponge was washed and dried to obtain substrate@PDA;

[0012] Benzoic acid is dissolved in N,N-dimethylformamide to obtain a solution, a fluorine-containing functional group compound, a carboxyl functional group compound and zirconium tetrachloride are added to the obtained solution, ultrasonically treated, and then the substrate@PDA is added thereto, heated to react, and after the reaction is completed, the obtained material is washed and dried to obtain a superhydrophobic MOF-UiO-67-F4 / MS material.

[0013] The composite structure of MOF and sponge substrate achieves functional complementarity. The high porosity and elasticity of the sponge provide good support for MOF, while the multi-level pore structure and hydrophobicity of MOF significantly improve the adsorption performance of the sponge. This composite structure enables the material to better maintain structural integrity during the adsorption process and can be reused many times.

[0014] Furthermore, the standing condition is: standing at room temperature for 6 hours.

[0015] Furthermore, the heating reaction conditions are: heating at 100° C. for 24 hours.

[0016] The third object of the present invention is to provide an application of a super-hydrophobic MOF-UiO-67-F4 / MS material in the field of oil-water separation.

[0017] The MOF-UiO-67-F4 metal organic framework material introduced in the present invention has a multi-level pore structure, can achieve a good oil-water separation effect, and contains fluorine functional groups, which increases the hydrophobicity of the material and improves its oil-water separation performance.

[0018] A fourth object of the present invention is to provide an application of a super-hydrophobic MOF-UiO-67-F4 / MS material in the removal of organic pollutants.

[0019] The present invention bonds a novel super-hydrophobic MOF-UiO-67-F4 material on the sponge surface by a self-assembly method, and is used as an adsorbent material for adsorbing and removing environmental organic pollutants. As an adsorbent material, MOF-UiO-67-F4 / MS inherits the excellent properties of MOF-UiO-67 / MS material and MOF-UiO-66-F4 / MS material, and adds a multi-level pore structure and hydrophobic groups, has a high surface area-volume ratio, excellent structural stability, is easy to prepare, and the raw materials are cheap and easy to obtain, non-toxic and pollution-free, and the like. At the same time, MOF-UiO-67-F4 increases the hydrophobicity of the material, which is beneficial to improving the oil-water separation performance. The preparation process is simple, easy to operate, and does not require an anaerobic environment or complex instruments.

[0020] Furthermore, the organic pollutants include o-dichlorobenzene, chloroform, petroleum ether, dimethyl silicone oil, rapeseed oil, dichloromethane, gasoline, pure crude oil and diluted crude oil.

[0021] Compared with the prior art, the present invention has the following advantages and technical effects:

[0022] 1) The preparation process of the method of the present invention is simple, easy to operate, and does not require an anaerobic environment or complex instruments. The MOF-UiO-67-F4 material obtained by bonding on the sponge surface by a one-step method has a multi-level pore structure, contains hydrophobic groups, can efficiently adsorb environmental organic pollutants, and has good reproducibility and repeatable practical performance, which provides the possibility for the industrial production of the material.

[0023] 2) The composite material provided by the present invention has good acid-base stability, can be reused many times, and the raw materials used are cheap and easily available, which can greatly reduce the cost of use.

[0024] 3) The substrate used in the preparation process of the present invention is non-toxic and non-polluting, has significant environmental advantages, and can actively respond to the call of green chemistry. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0026] Figure 1 This is a comparison chart of the adsorption effects of MOF-UiO-67-F4 / MS material, MOF-UiO-67 / MS material and MOF-UiO-66-F4 / MS material on different pollutants;

[0027] Figure 2 This is a performance diagram of the MOF-UiO-67-F4 / MS material prepared in Example 1 for repeated use of o-dichlorobenzene, chloroform, dichloromethane and gasoline;

[0028] Figure 3 This is a graph showing the phenomenon of the MOF-UiO-67-F4 / MS material prepared in Example 1 in aqueous solutions of different pH values ​​and salt solutions of different concentrations. DETAILED DESCRIPTION

[0029] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0030] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0031] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0032] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0033] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0034] The invention discloses a novel super-hydrophobic MOF-UiO-67-F4 / MS material as an adsorption material and a preparation method and application thereof. The MOF-UiO-67-F4 / MS material is formed by self-assembly of tetrafluoroterephthalic acid ligands containing fluorine functional groups, 4,4'-biphenyldicarboxylic acid ligands containing carboxyl groups and zirconium tetrachloride containing coordinated zirconium ions at 100°C by bonding a layer of functional groups on a sponge; benzoic acid is used as a morphology regulator in the preparation process to improve the crystal strength. The material is formed by a one-step reaction at 100°C, and the preparation process is simple and easy to operate. MOF-UiO-67-F4 / MS has a multi-level pore structure and contains a hydrophobic functional group of fluorine atoms. Compared with MOF-UiO-67 / MS and MOF-UiO-66-F4 / MS materials, the adsorption capacity of MOF-UiO-67-F4 / MS for environmental organic pollutants is greatly increased, and the adsorption performance is 1.08-1.32 times that of MOF-UiO-67 / MS materials and 1.12-1.55 times that of MOF-UiO-66-F4 / MS materials. The preparation process of the present invention is simple, and the obtained super-hydrophobic MOF-UiO-67-F4 / MS material has a super-good adsorption capacity for environmental organic pollutants, and has good stability and is easy to regenerate, can be repeatedly used, and the raw materials used for preparation are cheap and easy to obtain, non-toxic and pollution-free, and have good application prospects in the fields of oil-water separation and adsorption and removal of environmental organic pollutants.

[0035] The embodiment of the present invention provides a method for preparing a super-hydrophobic MOF-UiO-67-F4 / MS material, comprising the following steps:

[0036] 1) Disperse dopamine hydrochloride in Tris buffer, immerse the cleaned sponge (MS) therein, and let it stand (polymerization reaction occurs), then wash the obtained sponge and dry it to obtain substrate@PDA;

[0037] 2) dissolving benzoic acid in N,N-dimethylformamide to obtain a solution, adding a fluorine-containing functional group compound, a carboxyl functional group compound and zirconium tetrachloride to the obtained solution, ultrasonically treating the solution, and then adding the substrate@PDA thereto, heating to react, and after the reaction is completed, washing the obtained material and drying it to obtain a superhydrophobic MOF-UiO-67-F4 / MS material.

[0038] In some feasible embodiments, the concentration of the fluorine-containing functional group compound tetrafluoroterephthalic acid is 0.01-0.03 M, that is, the concentration of tetrafluoroterephthalic acid in the obtained N,N-dimethylformamide is 0.01-0.03 M. Exemplarily, in the following embodiments of the present invention, the concentration of tetrafluoroterephthalic acid in N,N-dimethylformamide can be set to 0.02 M.

[0039] In some feasible embodiments, the concentration of the carboxyl functional group-containing compound 4,4'-biphenyl dicarboxylic acid is 0.01-0.03 M, that is, the concentration of 4,4'-biphenyl dicarboxylic acid in N,N-dimethylformamide is 0.01-0.03 M. Exemplarily, in the following embodiments of the present invention, the concentration of 4,4'-biphenyl dicarboxylic acid in N,N-dimethylformamide can be set to 0.02 M.

[0040] The molar ratio of tetrafluoroterephthalic acid to 4,4'-biphenyldicarboxylic acid is 1:1.

[0041] In some feasible embodiments, the concentration of zirconium tetrachloride is 0.0068-0.02 M, that is, the concentration of zirconium tetrachloride in N,N-dimethylformamide is 0.0068-0.02 M. Exemplarily, in the following embodiments of the present invention, the concentration of zirconium tetrachloride in N,N-dimethylformamide can be set to 0.01375 M.

[0042] In some feasible embodiments, the standing condition is: standing at room temperature for 6 hours.

[0043] In some feasible embodiments, the heating reaction condition is: heating at 100° C. for 24 hours.

[0044] In some feasible embodiments, the washing is performed by washing with deionized water and ethanol three times respectively.

[0045] In some feasible embodiments, the drying is: drying at 60° C. for 24 hours.

[0046] The above preparation method can also be used to prepare a super-hydrophobic MOF-UiO-67-F4 / MS material. Due to the multi-level pore structure and strong hydrophobic and lipophilic groups, the adsorption multiple of organic pollutants by the material as an oil-water separation material is 1.08-1.32 times that of MOF-UiO-67 / MS material and 1.12-1.55 times that of MOF-UiO-66-F4 / MS material.

[0047] The prepared superhydrophobic MOF-UiO-67-F4 / MS material can be used in the field of oil-water separation.

[0048] The prepared super-hydrophobic MOF-UiO-67-F4 / MS material can be used in the removal of organic pollutants, including o-dichlorobenzene, chloroform, petroleum ether, dimethyl silicone oil, rapeseed oil, dichloromethane, gasoline, pure crude oil and diluted crude oil (pure crude oil and acetone mixed in a volume ratio of 1:1).

[0049] The "room temperature" mentioned in the present invention refers to 25±2°C unless otherwise specified.

[0050] The raw materials used in the present invention are all purchased from the market. Tetrafluoroterephthalic acid, 4,4'-biphenyldicarboxylic acid and zirconium tetrachloride in the examples are all purchased from Jilin Yanshen Technology Co., Ltd.; DMF is purchased from Tiandi Co., Ltd., USA.

[0051] The technical solution of the present invention is further illustrated by the following embodiments.

[0052] Example 1

[0053] A method for preparing a super-hydrophobic MOF-UiO-67-F4 / MS material comprises the following steps:

[0054] 1) Preparation of substrate@PDA:

[0055] Dopamine hydrochloride (10.0 mg) was dispersed in Tris buffer (10 mM, 40 mL) and sonicated for 5 min to obtain a solution;

[0056] The sponge (MS) was washed three times with deionized water and ethanol respectively, and dried to obtain a clean sponge;

[0057] The cleaned sponge was immersed in the obtained solution and allowed to stand at room temperature for 6 h, and then the obtained sponge was washed with deionized water and ethanol three times respectively, and dried at 60 °C for 24 h to obtain substrate@PDA;

[0058] 2) Preparation of MOF-UiO-67-F4 / MS materials

[0059] 1.34 g of benzoic acid (1.1 mmol) was dissolved in 80 mL of N,N-dimethylformamide (DNF), and dissolved by ultrasonication until completely clear and transparent to obtain a solution;

[0060] 0.4 g of 4,4'-biphenyldicarboxylic acid (1.65 mmol, CAS: 787-70-2), 0.393 g of tetrafluoroterephthalic acid (1.65 mmol, CAS: 652-36-8), and 0.256 g of zirconium tetrachloride (1.1 mmol) were weighed into the obtained solution, and ultrasonic treatment was performed for 30 min until completely dissolved. Then, the substrate@PDA obtained in step 1) was added thereto, ultrasonicated for 5 min, and then heated at 100°C for 24 h. The obtained material was rinsed with ethanol and dried at 60°C for 24 h to obtain a superhydrophobic MOF-UiO-67-F4 / MS material.

[0061] Comparative Example 1

[0062] A method for preparing a MOF-UiO-67 / MS material comprises the following steps:

[0063] 1) Preparation of substrate@PDA:

[0064] Dopamine hydrochloride (10.0 mg) was dispersed in Tris buffer (10 mM, 40 mL) and sonicated for 5 min to obtain a solution;

[0065] The sponge (MS) was washed three times with deionized water and ethanol respectively, and dried to obtain a clean sponge;

[0066] The cleaned sponge was immersed in the obtained solution and allowed to stand at room temperature for 6 h, and then the obtained sponge was washed with deionized water and ethanol three times respectively, and dried at 60 °C for 24 h to obtain substrate@PDA;

[0067] 2) Preparation of MOF-UiO-67 / MS materials

[0068] Dissolve 1.34 g of benzoic acid in 80 mL of N,N-dimethylformamide (DNF) and dissolve by ultrasonic until completely clear and transparent to obtain a solution;

[0069] 0.8 g of 4,4'-biphenyldicarboxylic acid (3.30 mmol, CAS: 787-70-2) and 0.256 g of zirconium tetrachloride (1.1 mmol) were weighed into the obtained solution and ultrasonically treated for 30 min until completely dissolved. Then, the substrate@PDA obtained in step 1) was added thereto, ultrasonicated for 5 min and then heated at 100°C for 24 h. The obtained material was rinsed with ethanol and dried at 60°C for 24 h to obtain MOF-UiO-67 / MS material.

[0070] Comparative Example 2

[0071] A method for preparing a MOF-UiO-66-F4 / MS material comprises the following steps:

[0072] 1) Preparation of substrate@PDA:

[0073] Dopamine hydrochloride (10.0 mg) was dispersed in Tris buffer (10 mM, 40 mL) and sonicated for 5 min to obtain a solution;

[0074] The sponge (MS) was washed three times with deionized water and ethanol respectively, and dried to obtain a clean sponge;

[0075] The cleaned sponge was immersed in the obtained solution and allowed to stand at room temperature for 6 h, and then the obtained sponge was washed with deionized water and ethanol three times respectively, and dried at 60 °C for 24 h to obtain substrate@PDA;

[0076] 2) Preparation of MOF-UiO-66-F4 / MS materials

[0077] 0.476 g of tetrafluoroterephthalic acid (2.0 mmol, CAS: 652-36-8) and 0.930 g of zirconium tetrachloride (4.0 mmol) were weighed into 60 mL of ethanol solution and dissolved by ultrasonication until completely clear and transparent. Then, the substrate@PDA obtained in step 1) was added thereto. After ultrasonication for 5 min, the mixture was heated at 120 °C for 24 h. The obtained material was rinsed with ethanol and dried at 60 °C for 24 h to obtain MOF-UiO-66-F4 / MS material.

[0078] Application Example 1

[0079] The materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 were used as adsorbents to carry out an adsorption performance test. The specific method is as follows: a piece of material (1.0×1.0×1.0 cm) was weighed and the mass m was recorded. 1 Then, it was immersed in o-dichlorobenzene, chloroform, petroleum ether, dimethyl silicone oil, rapeseed oil, dichloromethane, gasoline, pure crude oil, and diluted crude oil (pure crude oil: acetone = 1:1) for full adsorption for 2 minutes. After reaching full saturation, it was taken out and the mass m after adsorption was immediately weighed. 2 The experiment was repeated three times for each organic solvent, and the average value was calculated as the adsorption amount (Q, g / g) of the adsorbent for a certain organic solvent. The adsorption amount was determined using the following equation:

[0080]

[0081] Figure 1 This is a comparison chart of the adsorption effects of the materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 on different pollutants. It can be seen from the figure that the super hydrophobic MOF-UiO-67-F4 / MS material prepared in Example 1 as an oil-water separation material has an adsorption multiple of organic pollutants that is 1.08-1.32 times that of the MOF-UiO-67 / MS material and 1.12-1.55 times that of the MOF-UiO-66-F4 / MS material. Analysis shows that the reason may be due to the multi-level pore structure and strong hydrophobic and lipophilic groups.

[0082] Application Example 2

[0083] The reusability of MOF-UiO-67-F4 / MS prepared in Example 1 was tested. The specific method was as follows: a piece of MOF-UiO-67-F4 / MS material (1.0×1.0×1.0 cm) prepared in Example 1 was weighed and the mass m was recorded. 1 Then, it was immersed in o-dichlorobenzene, chloroform, dichloromethane, and gasoline for 2 minutes to fully adsorb. After reaching full saturation, it was taken out and the mass m after adsorption was immediately weighed. 2Subsequently, it was washed and dried, and the experiment was repeated using the block material in this way to determine the adsorption capacity (Q, g / g) of a certain organic solvent by MOF-UiO-67-F4 / MS after 10 times of repeated use. The adsorption capacity was determined using the following equation:

[0084]

[0085] Figure 2 This is a performance diagram of the MOF-UiO-67-F4 / MS material prepared in Example 1 for repeated use of o-dichlorobenzene, chloroform, dichloromethane and gasoline. The experimental results show that the superhydrophobic MOF-UiO-67-F4 / MS material prepared by this method exhibits good adsorption performance, can efficiently adsorb organic pollutants in the environment, and at the same time exhibits excellent reproducibility and reusability, and has good application prospects.

[0086] Application Example 3

[0087] The acid-base stability of MOF-UiO-67-F4 / MS prepared in Example 1 was tested. The specific method was as follows: aqueous solutions with pH values ​​of 1.0, 3.0, 5.0, 9.0, 10.0, and 11.0 and salt solutions with NaCl concentrations of 1.0 mol / L, 1.5 mol / L, 2.0 mol / L, and 2.5 mol / L were prepared, and the MOF-UiO-67-F4 / MS material (1.0×1.0×1.0 cm) prepared in Example 1 was placed in the 10 prepared solutions, respectively, and allowed to stand for 24 hours to observe the suspension of the material.

[0088] Figure 3 The diagram shows the phenomenon of the MOF-UiO-67-F4 / MS material prepared in Example 1 in aqueous solutions of different pH values ​​and salt solutions of different concentrations. The experimental phenomena show that the super-hydrophobic MOF-UiO-67-F4 / MS material prepared in Example 1 has acid-base stability, and can extend its service life and expand its scope of use.

[0089] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A super hydrophobic MOF-UiO-67-F4 / MS material, characterized in that: The superhydrophobic MOF-UiO-67-F4 / MS material was prepared by a solvothermal method using fluorine-containing functional group compounds and carboxyl-containing functional group compounds as ligands, zirconium tetrachloride as a metal source, N,N-dimethylformamide as a solvent, and benzoic acid as a morphology regulator. in, The fluorine-containing functional group compound is tetrafluoroterephthalic acid; The carboxyl functional group-containing compound is 4,4'-biphenyldicarboxylic acid.

2. The super-hydrophobic MOF-UiO-67-F4 / MS material according to claim 1, characterized in that The molar ratio of the tetrafluoroterephthalic acid to the 4,4'-biphenyldicarboxylic acid is 1:

1.

3. The super-hydrophobic MOF-UiO-67-F4 / MS material according to claim 1, characterized in that The molar ratio of the zirconium tetrachloride to the ligand is 1:

3.

4. The super-hydrophobic MOF-UiO-67-F4 / MS material according to claim 1, characterized in that The molar ratio of the benzoic acid to the zirconium tetrachloride is 1:

1.

5. The method for preparing the super-hydrophobic MOF-UiO-67-F4 / MS material according to any one of claims 1 to 4, characterized in that: The following steps are involved: Dopamine hydrochloride is dispersed in Tris buffer, a cleaned melamine sponge is immersed therein, and allowed to stand, and then the obtained sponge is washed and dried to obtain substrate@PDA; Benzoic acid is dissolved in N,N-dimethylformamide to obtain a solution, a fluorine-containing functional group compound, a carboxyl functional group compound and zirconium tetrachloride are added to the obtained solution, ultrasonically treated, and then the substrate@PDA is added thereto, heated to react, and after the reaction is completed, the obtained material is washed and dried to obtain a superhydrophobic MOF-UiO-67-F4 / MS material.

6. The method for preparing the super-hydrophobic MOF-UiO-67-F4 / MS material according to claim 5, characterized in that: The static condition is: leaving at room temperature for 6 hours.

7. The method for preparing the super-hydrophobic MOF-UiO-67-F4 / MS material according to claim 6, characterized in that: The heating reaction conditions are: heating at 100° C. for 24 h.

8. Application of the super-hydrophobic MOF-UiO-67-F4 / MS material according to any one of claims 1 to 4 in the field of oil-water separation.

9. Use of the super-hydrophobic MOF-UiO-67-F4 / MS material according to any one of claims 1 to 4 in removing organic pollutants.

10. The use according to claim 9, characterized in that: The organic pollutants include o-dichlorobenzene, chloroform, petroleum ether, dimethyl silicone oil, rapeseed oil, dichloromethane, gasoline, pure crude oil and diluted crude oil.

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