CN113877541B - High-load ZIF-67 film material and preparation method thereof - Google Patents
High-load ZIF-67 film material and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0265—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries extraction by solid resins
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Abstract
The invention relates to the technical field of membrane materials, in particular to a high-load ZIF-67 membrane material and a preparation method thereof. The preparation method of the high-load ZIF-67 film material comprises the following steps: a) Grafting maleic anhydride on the surface of the polymer substrate material by adopting a co-radiation grafting method to obtain a polymer substrate material grafted with maleic anhydride; b) Mixing metal salt, an organic ligand, a solvent and a polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a high-load ZIF-67 film; the metal salt is cobalt salt; the solvent includes methanol or water. The high-load ZIF-67 film material provided by the invention can be used for extracting uranium from seawater, and in the process of extracting uranium from seawater, imidazole groups can be complexed with uranyl ions, and meanwhile, cobalt has an affinity effect on the uranyl ions, so that the adsorption of the high-load ZIF-67 film material on uranium is facilitated, and the uranium adsorption performance of the high-load ZIF-67 film material is excellent.
Description
Technical Field
The invention relates to the technical field of membrane materials, in particular to a high-load ZIF-67 membrane material and a preparation method thereof.
Background
In recent years, with the progress of human society technology and the rapid development of industry, energy consumption is growing increasingly, so that fossil fuel resources are becoming scarce, and environmental problems such as serious greenhouse effect and global warming caused by excessive combustion of fossil fuel are also caused, so that the problem of energy shortage and environmental pollution is always the subject of the era. Nuclear energy is considered as a new clean energy source, and is the optimal energy source for replacing fossil energy sources. Uranium is the most predominant dye in nuclear fission reactors, however, the worldwide developable ore uranium resources are very limited, only one thousandth of the uranium reserves in seawater. At present, the uranium ore production in China cannot meet the requirements, and more than 70% of uranium ore production needs to be imported. Therefore, the development of the efficient and economic technology for extracting uranium from seawater has important significance.
The technology for extracting uranium from seawater mainly comprises a liquid phase extraction method, a chemical precipitation method, an ion exchange method, an electrochemical method, an active microorganism enrichment method and the like. The research direction of extracting uranium from seawater is mainly focused on developing efficient uranium adsorption materials. The uranium adsorption material comprises an inorganic adsorbent, an organic adsorbent, a metal organic framework and the like. Among them, the polymer adsorbent is considered as one of the most promising materials for mass placement and application due to its good physical and chemical stability. At present, many countries have studied such adsorbent materials. For example, egawa et al treat polyacrylonitrile beads with hydroxylamine to form an amidoxime-functionalized polymeric adsorbent which reached an adsorption capacity of 450 μg/g after 130 days of continuous seawater contact and recovered an average of 82.9% uranium over 10 cycles. Tamada et al used Radiation Induced Grafting (RIGP) polypropylene fibers of polyamidoxime for uranium adsorption. Chai Zhifang et al achieve selective adsorption of uranium by introducing organic functional groups into the metal organic framework material MILs-101 at the development metal sites to functionalize the amino groups. A great deal of researches show that the application of the seawater uranium extraction adsorption material needs to meet the following characteristics: high adsorption capacity, high adsorption rate, high uranyl ion selectivity, good durability and easy elution. However, the polymer adsorbent has the problem of low adsorption speed at present, so that the time and cost for extracting uranium are greatly increased, and the uranium adsorption performance is required to be improved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a high-load ZIF-67 film material and a preparation method thereof, and the high-load ZIF-67 film material prepared by the invention has better uranium adsorption performance.
The invention provides a preparation method of a high-load ZIF-67 film material, which comprises the following steps:
a) Grafting maleic anhydride on the surface of the polymer substrate material by adopting a co-radiation grafting method to obtain a polymer substrate material grafted with maleic anhydride;
b) Mixing metal salt, an organic ligand, a solvent and a polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a high-load ZIF-67 film;
the metal salt is cobalt salt;
the solvent includes methanol or water.
Preferably, the polymer substrate material is a polymer non-woven fabric or a polymer porous membrane;
the polymer substrate material comprises at least one of UHMWPE, PP, PET, PTEF and PI.
Preferably, the co-radiation grafted radiation source comprises a cobalt 60 source or an electron accelerator;
the radiation dose of the co-radiation grafting is 5-100 kGy, and the radiation dose rate is 0.3-5 kGy/h;
the co-radiation grafting was performed at room temperature.
Preferably, grafting maleic anhydride on the surface of the polymer substrate material by adopting a co-radiation grafting method comprises the following steps:
in a sealed container, tetrahydrofuran solution of maleic anhydride is soaked in a high polymer substrate material, and after sealing, the mixture is put into a radiation source for co-radiation grafting;
after grafting, the grafting amount of maleic anhydride on the surface of the polymer substrate material is 25-40 nmol/cm 2 。
Preferably, the structure of the organic ligand is shown as a formula I;
in the formula I, X is selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, vinyl or ester groups.
Preferably, the molar ratio of the metal salt to the organic ligand is 1 to 1.5:1 to 2.
Preferably, the ratio of the molar total amount of the metal salt and the organic ligand to the surface area of the polymer base material grafted with maleic anhydride is 40 to 60. Mu. Mol/cm 2 。
Preferably, the pressure of the reaction is 1 to 1.5atm for 6 to 48 hours.
The invention also provides a high-load ZIF-67 film material prepared by the preparation method.
The invention provides a preparation method of a high-load ZIF-67 film material, which comprises the following steps: a) Grafting maleic anhydride on the surface of the polymer substrate material by adopting a co-radiation grafting method to obtain a polymer substrate material grafted with maleic anhydride; b) Mixing metal salt, an organic ligand, a solvent and a polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a high-load ZIF-67 film; the metal salt is cobalt salt; the solvent includes methanol or water. The high-load ZIF-67 membrane material provided by the invention can be used for extracting uranium from seawater, and in the process of extracting uranium from seawater, imidazole groups can be complexed with uranyl ions, and meanwhile, cobalt has an affinity effect on the uranyl ions, so that the adsorption of the high-load ZIF-67 membrane material on uranium is facilitated. Experimental results show that the high-load ZIF-67 membrane material provided by the invention can remove more than 91.8% of uranium in a solution under extremely low uranium concentration (less than or equal to 3.3 ppb) through 2 times of circulating filtration, so that the rapid high-selectivity uranium extraction is realized, the membrane material is easy to recycle and post-treat, and the durability is good, and therefore, the high-load ZIF-67 membrane material for ultra-fast seawater uranium extraction provided by the invention has a good application prospect.
Drawings
FIG. 1 is an SEM image of a high load ZIF-67 film of example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a high-load ZIF-67 film material, which comprises the following steps:
a) Grafting maleic anhydride on the surface of the polymer substrate material by adopting a co-radiation grafting method to obtain a polymer substrate material grafted with maleic anhydride;
b) Mixing metal salt, an organic ligand, a solvent and a polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a high-load ZIF-67 film;
the metal salt is cobalt salt;
the solvent includes methanol or water.
The method firstly adopts a co-radiation grafting method to graft maleic anhydride on the surface of the high polymer substrate material. In certain embodiments of the present invention, grafting maleic anhydride onto the surface of a polymeric substrate material using a co-radiation grafting process comprises:
in a sealed container, tetrahydrofuran solution of maleic anhydride is put into a radiation source after being soaked by a polymer base material and sealed, and co-radiation grafting is carried out.
In certain embodiments of the present invention, before the tetrahydrofuran solution of maleic anhydride is passed through the polymeric substrate material, further comprising:
and ultrasonically cleaning the polymer substrate material with acetone, and drying.
The process parameters of the ultrasonic cleaning are not particularly limited, and those well known to those skilled in the art may be used.
In certain embodiments of the invention, the drying temperature is 55-65 ℃.
In certain embodiments of the invention, the sealed container is an aluminum foil bag.
In certain embodiments of the invention, the concentration of the tetrahydrofuran solution of maleic anhydride is from 1.0 to 1.5g/mL. In certain embodiments, the concentration of the tetrahydrofuran solution of maleic anhydride is 1.5g/mL.
In certain embodiments of the present invention, the polymeric substrate material is a polymeric nonwoven fabric or a polymeric porous membrane. The polymer substrate material comprises at least one of UHMWPE, PP, PET, PTEF and PI. The thickness of the polymer-based base material was 0.42mm.
In certain embodiments of the invention, the co-radiation grafted radiation source comprises a cobalt 60 source or an electron accelerator, the co-radiation grafted radiation dose is in the range of 5 to 100kGy and the radiation dose rate is in the range of 0.3 to 5kGy/h. In certain embodiments, the radiation dose of the co-radiation grafting is 5kGy. In certain embodiments, the co-radiation grafted radiation dose rate is 0.6kGy/h.
In certain embodiments of the invention, the co-radiation grafting is performed at room temperature.
In certain embodiments of the present invention, after the co-radiation grafting, further comprising: ultrasonic cleaning and drying. The ultrasonic cleaning is sequentially carried out by adopting tetrahydrofuran and ethanol. The process parameters of the ultrasonic cleaning are not particularly limited, and those well known to those skilled in the art may be used. The drying temperature is 55-65 ℃.
In some embodiments of the present invention, the grafting amount of maleic anhydride on the surface of the polymeric substrate material after the co-irradiation grafting is 25 to 40nmol/cm 2 . In some embodiments, the grafting amount of the maleic anhydride on the surface of the polymer substrate material is 26.70nmol/cm 2 。
And after the co-radiation grafting is finished, a ZIF-67 layer is grown on the surface of the polymer substrate material grafted with maleic anhydride in situ, so that the high-load ZIF-67 film is obtained.
Specifically, the in-situ growth of the ZIF-8 layer on the surface of the polymer substrate material grafted with maleic anhydride comprises the following steps:
mixing metal salt, organic ligand, solvent and polymer base material grafted with maleic anhydride, and reacting at 15-40 deg.c to obtain high load ZIF-67 film.
Preferably, the method comprises the steps of:
dissolving metal salt in part of solvent to obtain a first solution;
dissolving an organic ligand in the residual solvent to obtain a second solution;
and after uniformly mixing the first solution and the second solution, putting the polymer substrate material grafted with maleic anhydride into the uniformly mixed solution, and reacting at 15-40 ℃ to obtain the high-load ZIF-67 film.
In the present invention, the metal salt is cobalt salt, and may be Co (NO 3 ) 2 ·6H 2 O。
In certain embodiments of the invention, the organic ligand has a structure according to formula I;
in the formula I, X is selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, vinyl or ester groups.
In certain embodiments, the organic ligand is 2-methylimidazole.
In certain embodiments of the invention, the solvent comprises methanol or water.
In certain embodiments of the invention, the molar ratio of the metal salt to the organic ligand is from 1 to 1.5:1 to 2. In certain embodiments, the molar ratio of metal salt to organic ligand is 1:1. 1.2:1 or 1:1.2.
in certain embodiments of the invention, the metal salt and the portion of solvent are used in an amount ratio of 0.005 to 0.015mol:50mL. In certain embodiments, the metal salt and the portion of solvent are present in an amount ratio of 0.01mol:50mL or 0.012mol:50mL.
In certain embodiments of the invention, the ratio of the organic ligand to the remaining solvent is from 0.003 to 0.03mol: 50-200 mL. In certain embodiments, the ratio of the organic ligand to the remaining solvent is 0.01mol:200mL or 0.012mol:200mL.
In certain embodiments of the invention, the ratio of the molar sum of the metal salt and the organic ligand to the surface area of the polymeric substrate material grafted with maleic anhydride is from 40 to 60. Mu. Mol/cm 2 . In certain embodiments, the ratio of the molar sum of the metal salt and the organic ligand to the surface area of the polymeric substrate material grafted with maleic anhydride is 49.97. Mu. Mol/cm 2 、54.95μmol/cm 2 Or 54.84. Mu. Mol/cm 2 。
In certain embodiments of the invention, the temperature of the reaction is 20 to 30 ℃. In certain embodiments, the temperature of the reaction is 25 ℃.
In certain embodiments of the invention, the pressure of the reaction is 1 to 1.5atm. In certain embodiments, the pressure of the reaction is 1atm.
In certain embodiments of the invention, the reaction time is from 6 to 48 hours. In certain embodiments, the reaction time is 24 hours.
In certain embodiments of the present invention, after the reacting, further comprising: cleaning and drying. The cleaning is performed by methanol. The drying temperature is 55-65 ℃.
After the co-radiation grafting is finished, the ZIF-67 layer is directly grown on the surface of the high polymer substrate material grafted with maleic anhydride in situ, and an intermediate layer such as a molecular sieve intermediate layer or a zinc oxide coating is not required to be additionally introduced.
In the invention, maleic anhydride is directly grafted on the surface of the polymer base material by adopting a co-radiation grafting method, the maleic anhydride can form a covalent bond with the polymer base material, and ZIF-67 grows by taking maleic anhydride as a nucleation point, so that the ZIF-67 film can be firmly combined with the surface of the base material. According to the invention, continuous defect-free membranes with different loading amounts can be prepared by regulating the grafting amount of the maleic anhydride on the surface and the ratio of reactants through theoretical calculation, which has important significance for membrane separation.
In the preparation method of the high-load ZIF-67 film material, high-temperature roasting (> 300 ℃) is not needed, and the preparation condition is mild, so that the preparation method is suitable for various polymer substrates.
The high-load ZIF-67 film material prepared by the invention has better uranium adsorption capacity and selectivity. And the ZIF-67 layer is directly grown on the surface of the polymer substrate material grafted with maleic anhydride in situ, so that the stability of the material is improved. The microporous structure of the polymer substrate material only plays a supporting role on the ZIF-67 layer with nanometer thickness without affecting the flux of the ZIF-67 layer, so that the liquid permeation speed is greatly improved, and the uranium extraction speed is increased.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
The invention also provides a high-load ZIF-67 film material prepared by the preparation method. In certain embodiments of the present invention, the high load ZIF-67 membrane material comprises ZIF-67 particles that are closely packed on and cover the surface of the nonwoven fabric. In certain embodiments of the present invention, the ZIF-67 particle size is between 50 and 200 nm.
The high-load ZIF-67 membrane material provided by the invention can be used for extracting uranium from seawater, and in the process of extracting uranium from seawater, imidazole groups can be complexed with uranyl ions, and meanwhile, cobalt has an affinity effect on the uranyl ions, so that the adsorption of the high-load ZIF-67 membrane material on uranium is facilitated. Experimental results show that the high-load ZIF-67 film material provided by the invention can remove more than 91.8% of uranium in the solution through 2 times of circulating filtration under extremely low uranium concentration (less than or equal to 3.3 ppb). The high-load ZIF-67 membrane material for extracting uranium from ultra-fast seawater has good application prospect.
In order to further illustrate the present invention, the following examples are provided to illustrate a high load ZIF-67 membrane material and a method for preparing the same, but should not be construed as limiting the scope of the present invention.
The reagents used in the examples below are all commercially available.
Example 1
A polypropylene (PP) nonwoven fabric of 0.42mm thickness was ultrasonically cleaned in acetone, dried at 60 ℃ and packed into an aluminum foil bag. Quality of preparationAnd then adding the tetrahydrofuran solution of maleic anhydride and the polypropylene non-woven fabric into an aluminum foil bag, completely immersing the polypropylene non-woven fabric into the maleic anhydride solution, thermoplastic sealing the aluminum foil bag, and placing the aluminum foil bag into a radiation source (an electron accelerator) for irradiation at room temperature, wherein the radiation dose rate is 0.6kGy/h and the radiation dose is 5kGy. Ultrasonic cleaning the irradiated polypropylene non-woven fabric sequentially with tetrahydrofuran and ethanol solvent, and drying at 60 ℃ to obtain the maleic anhydride grafted polypropylene non-woven fabric with the maleic anhydride grafted surface density of 26.70nmol/cm 2 。
Example 2
Co (NO) 3 ) 2 ·6H 2 O (2.91 g, 0.010mol) was dissolved in 50mL of methanol to give a first solution; 2-methylimidazole (0.82 g, 0.010mol) was dissolved in 200mL of methanol to give a second solution; after the first solution and the second solution were mixed uniformly, 4 sheets of the maleic anhydride-grafted polypropylene nonwoven fabric prepared in example 1 (monolithic area 50X 200mm 2 ) Putting into the mixed solution, the Co (NO 3 ) 2 ·6H 2 The ratio of the molar total amount of O and 2-methylimidazole to the surface area of the maleic anhydride-grafted polypropylene nonwoven fabric was 49.97. Mu. Mol/cm 2 And (3) reacting for 24 hours at 25 ℃ and 1atm in a reaction kettle, after the reaction is finished, cleaning the non-woven fabric membrane by using methanol, and drying at 60 ℃ to obtain the high-load ZIF-67 membrane (HF-1).
Scanning electron microscopy analysis was performed on the high load ZIF-67 film (HF-1) obtained in example 2, and the results are shown in FIG. 1. FIG. 1 is an SEM image of a high load ZIF-67 film of example 2 of the present invention. As can be seen in FIG. 1, ZIF-67 particles are closely packed on a nonwoven substrate and cover the substrate to form a ZIF-67 film, with the ZIF-67 particles having a size between 50 and 200 nm. SEM results demonstrated that ZIF-67 membranes were successfully synthesized.
Digestion of the high load ZIF-67 film of example 2 with hydrofluoric acid, determination of the zinc ion content in the solution by ICP-MS, and calculation of the MOF load of 0.51mg/cm on the film surface 2 Thereby obtaining the high-load uranium extraction film (HF-1).
Example 3
Co (NO) 3 ) 2 ·6H 2 O (3.49 g,0.012 mol) was dissolved in 50mL of methanol to obtain a first solution; 2-methylimidazole (0.82 g, 0.010mol) was dissolved in 200mL of methanol to give a second solution; after the first solution and the second solution were mixed uniformly, 4 sheets of the maleic anhydride-grafted polypropylene nonwoven fabric prepared in example 1 (monolithic area 50X 200mm 2 ) Putting into the mixed solution, the Co (NO 3 ) 2 ·6H 2 The ratio of the molar total amount of O and 2-methylimidazole to the surface area of the maleic anhydride grafted polypropylene nonwoven fabric was 54.95. Mu. Mol/cm 2 And (3) reacting for 24 hours at 25 ℃ and 1atm in a reaction kettle, after the reaction is finished, cleaning the non-woven fabric membrane by using methanol, and drying at 60 ℃ to obtain the high-load ZIF-67 membrane (HF-2).
Digestion of the high load ZIF-67 film of example 3 with hydrofluoric acid, determination of the zinc ion content in the solution by ICP-MS, and calculation of the MOF load of 0.56mg/cm on the film surface 2 Thereby obtaining the high-load uranium extraction film (HF-2).
Example 4
Co (NO) 3 ) 2 ·6H 2 O (2.91 g, 0.010mol) was dissolved in 50mL of methanol to give a first solution; 2-methylimidazole (0.98 g,0.012 mol) was dissolved in 200mL of methanol to obtain a second solution; after the first solution and the second solution were mixed uniformly, 4 sheets of the maleic anhydride-grafted polypropylene nonwoven fabric prepared in example 1 (monolithic area 50X 200mm 2 ) Putting into the mixed solution, the Co (NO 3 ) 2 ·6H 2 The ratio of the molar total amount of O and 2-methylimidazole to the surface area of the maleic anhydride-grafted polypropylene nonwoven fabric was 54.84. Mu. Mol/cm 2 And (3) reacting for 24 hours at 25 ℃ and 1atm in a reaction kettle, after the reaction is finished, cleaning the non-woven fabric membrane by using methanol, and drying at 60 ℃ to obtain the high-load ZIF-67 membrane (HF-3).
Digestion of the high load ZIF-67 film of example 4 with hydrofluoric acid, determination of the zinc ion content in the solution by ICP-MS, and calculation of the MOF load of 0.47mg/cm on the film surface 2 Thereby obtaining the high-load uranium extraction film (HF-3).
Example 5
Research is carried out on uranium adsorption performance of the prepared high-load uranium extraction film HF-1: the uranium solution of 3.3ppb (concentration consistent with the concentration of uranium in seawater) was filtered with a high load uranium extraction membrane HF-1. The HF-1 film was cut into 35mm diameter discs, three discs were placed in a filter, and 1L uranium solution was filtered for 18min. After 2 times of filtration, the uranium concentration in the filtrate is detected by ICP-MS, and the result shows that the clearance rate of the uranium adsorption film to uranium in the solution reaches more than 93% through normal pressure filtration, and the excellent rapid uranium absorption performance is shown.
Example 6
Research is carried out on uranium adsorption performance of the prepared high-load uranium extraction film HF-2: the uranium solution of 3.3ppb (concentration consistent with the concentration of uranium in seawater) was filtered with a high load uranium extraction membrane HF-2. The HF-2 film was cut into 35mm diameter discs, three discs were placed in a filter, and 1L uranium solution was filtered for 18min. After 2 times of filtration, the uranium concentration in the filtrate is detected by ICP-MS, and the result shows that the clearance rate of the uranium adsorption film to uranium in the solution reaches more than 94.2% through normal pressure filtration, and excellent uranium adsorption performance is shown.
Example 7
Research is carried out on uranium adsorption performance of the prepared high-load uranium extraction film HF-3: the uranium solution of 3.3ppb (concentration consistent with the concentration of uranium in seawater) was filtered with a high load uranium extraction membrane HF-3. The HF-3 film was cut into 35mm diameter discs, three discs were placed in a filter, and 1L uranium solution was filtered for 18min. After 2 times of filtration, the uranium concentration in the filtrate is detected by ICP-MS, and the result shows that the clearance rate of the uranium adsorption film to uranium in the solution reaches more than 91.8% through normal pressure filtration, and excellent uranium adsorption performance is shown.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a high-load ZIF-67 film material comprises the following steps:
a) Grafting maleic anhydride on the surface of the polymer substrate material by adopting a co-radiation grafting method to obtain a polymer substrate material grafted with maleic anhydride;
b) Mixing metal salt, an organic ligand, a solvent and a polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a high-load ZIF-67 film;
the metal salt is cobalt salt;
the solvent comprises methanol or water;
the polymer substrate material is a polymer non-woven fabric or a polymer porous membrane.
2. The method according to claim 1, wherein the polymer base material is a polymer nonwoven fabric or a polymer porous film;
the polymer substrate material comprises at least one of UHMWPE, PP, PET, PTEF and PI.
3. The method of claim 1, wherein the co-radiation grafted radiation source comprises a cobalt 60 source or an electron accelerator;
the radiation dose of the co-radiation grafting is 5-100 kGy, and the radiation dose rate is 0.3-5 kGy/h;
the co-radiation grafting was performed at room temperature.
4. The method of claim 1, wherein grafting maleic anhydride on the surface of the polymeric substrate material by co-radiation grafting comprises:
in a sealed container, tetrahydrofuran solution of maleic anhydride is soaked in a high polymer substrate material, and after sealing, the mixture is put into a radiation source for co-radiation grafting;
after grafting is completed, the surface of the polymer substrate material is horseThe grafting amount of the maleic anhydride is 25-40 nmol/cm 2 。
5. The preparation method according to claim 1, wherein the organic ligand has a structure shown in formula I;
a formula I;
in the formula I, X is methyl.
6. The preparation method according to claim 1, wherein the molar ratio of the metal salt to the organic ligand is 1 to 1.5: 1-2.
7. The preparation method according to claim 1, wherein the ratio of the molar total amount of the metal salt and the organic ligand to the surface area of the polymer base material grafted with maleic anhydride is 40 to 60 [ mu ] mol/cm 2 。
8. The method according to claim 1, wherein the pressure of the reaction is 1 to 1.5atm for 6 to 48 hours.
9. The high-load ZIF-67 film material prepared by the preparation method of any one of claims 1-8.
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