CN113813925A - Continuous ZIF-67 membrane material and preparation method thereof - Google Patents

Continuous ZIF-67 membrane material and preparation method thereof Download PDF

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CN113813925A
CN113813925A CN202111211036.0A CN202111211036A CN113813925A CN 113813925 A CN113813925 A CN 113813925A CN 202111211036 A CN202111211036 A CN 202111211036A CN 113813925 A CN113813925 A CN 113813925A
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maleic anhydride
substrate material
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邓鹏飏
张依帆
高健
郑春柏
魏巍
柳美华
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to the technical field of membrane materials, in particular to a continuous ZIF-67 membrane material and a preparation method thereof. The preparation method of the continuous ZIF-67 membrane material comprises the following steps: A) calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 membrane material through a formula (1); B) according to the calculation result of the step A), maleic anhydride is grafted 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; C) mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a continuous ZIF-8 membrane material; the metal salt is cobalt salt; the solvent includes methanol or water. The prepared film is a continuous defect-free film, uranyl ions are removed by separating the uranyl ions and the affinity of imidazole groups for the uranyl ions based on the ZIF-8 size effect, and the uranyl ions and the imidazole groups have synergistic effect and relatively excellent uranium adsorption performance.

Description

Continuous ZIF-67 membrane material and preparation method thereof
Technical Field
The invention relates to the technical field of membrane materials, in particular to a continuous ZIF-67 membrane material and a preparation method thereof.
Background
In recent years, with scientific and technological progress of human society and rapid development of industry, energy consumption is increasing, fossil fuel resources are becoming scarce day by day, and excessive combustion of fossil fuels also causes serious environmental problems such as greenhouse effect and global warming, so that solving of energy shortage and environmental pollution is always the theme of the times. Nuclear energy, as a new clean energy source, is considered as the optimal energy source to replace fossil energy. Uranium is the most prominent dye in nuclear fission reactors, however, the worldwide exploitable ore uranium resource is very limited, being only one in a thousand of the uranium reserves in seawater. At present, the uranium ore production in China cannot meet the demand, and more than 70% of uranium ore needs to be imported. Therefore, the development of the efficient and economic technology for extracting uranium from seawater is of great 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 current research direction of extracting uranium from seawater mainly focuses on developing high-efficiency uranium adsorption materials. The uranium adsorbent material includes an inorganic adsorbent, an organic adsorbent, a metal organic framework, and the like. Among them, the polymer adsorbent is recognized as one of the most promising materials to be placed and applied on a large scale due to its superior physical and chemical stability. Currently, many countries have studied such adsorbent materials. Treatment of polyacrylonitrile beads with hydroxylamine, such as Egawa, resulted in an amidoxime-functionalized polymeric adsorbent having an adsorption capacity of 450 pg/g after 130 days of continuous seawater exposure and an average recovery of 82.9% uranium over 10 cycles. Tamada et al use polypropylene fibers of Radiation Induced Grafting (RIGP) polyamidoxime for uranium adsorption. Faggar et al achieved selective adsorption of uranium by introducing organic functional groups on the developed metal sites in the metal organic framework material MIL-101 to functionalize their amino groups. A large number of researches show that the application of the uranium extraction adsorption material from seawater needs to meet the following characteristics: large adsorption capacity, high adsorption rate, high uranyl ion selectivity, good durability and easy elution. However, the polymer adsorbent has a problem of slow adsorption speed, which greatly increases the time and cost for extracting uranium, and the uranium adsorption performance is to be improved.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a continuous ZIF-67 membrane material and a preparation method thereof, and the prepared continuous ZIF-67 membrane material has excellent uranium adsorption performance.
The invention provides a preparation method of a continuous ZIF-67 membrane material, which comprises the following steps:
A) calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 membrane material through a formula (1);
Figure BDA0003308859690000021
in the formula (1), σmolarMaleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials2；
BET is the specific surface area of the polymeric substrate material, m2/g；
Rho is the mass areal density of the polymer substrate material, g/cm2；
A is an Avogastron constant;
a is the spacing, nm, between adjacent maleic anhydrides;
B) according to the calculation result of the step A), maleic anhydride is grafted 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;
C) mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a continuous ZIF-67 membrane material;
the metal salt is cobalt salt;
the solvent comprises methanol or water.
Preferably, the polymer substrate material is a polymer non-woven fabric or a polymer porous membrane;
the material of the high 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-irradiation grafting is carried out at room temperature.
Preferably, the grafting of maleic anhydride on the surface of the polymer substrate material by using a co-irradiation grafting method comprises:
in a sealed container, the tetrahydrofuran solution of maleic anhydride is immersed in the polymer substrate material, and after sealing, the polymer substrate material is put into a radiation source for carrying out co-radiation grafting.
Preferably, the structure of the organic ligand is shown as a formula I;
Figure BDA0003308859690000031
in formula I, X is selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, vinyl or ester group.
Preferably, the molar ratio of the metal salt to the organic ligand is 1-5: 1 to 1.2.
Preferably, the pressure of the reaction is 1-1.5 atm, and the time is 6-48 h.
The invention also provides a continuous ZIF-67 membrane material prepared by the preparation method.
The invention provides a preparation method of a continuous ZIF-67 membrane material, which comprises the following steps:
A) calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 membrane material through a formula (1);
Figure BDA0003308859690000032
in the formula (1), σmolarMaleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials2；
BET is the specific surface area of the polymeric substrate material, m2/g；
Rho is the mass areal density of the polymer substrate material, g/cm2；
A is an Avogastron constant;
a is the spacing, nm, between adjacent maleic anhydrides;
B) according to the calculation result of the step A), maleic anhydride is grafted 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;
C) mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a continuous ZIF-67 membrane material;
the metal salt is cobalt salt;
the solvent comprises methanol or water.
The film prepared by the preparation method is a continuous defect-free film, the aperture of ZIF-67 is the only channel for the uranyl ions to pass through, so that the uranyl ions are removed by separating the uranyl ions and the affinity of imidazole groups for the uranyl ions based on the ZIF-67 size effect, and the uranyl ions and the imidazole groups have a synergistic effect and have good removal performance for the uranyl ions. Therefore, the continuous ZIF-67 film material prepared by the method has better uranium adsorption performance. Experimental results show that the continuous ZIF-67 membrane material provided by the invention can remove more than 95.1% of uranium in the solution by 2 times of circulating filtration under an extremely low uranium concentration (less than or equal to 3.3 ppb). The continuous ZIF-67 film material for extracting uranium from ultrafast seawater provided by the invention has good application prospect.
Drawings
FIG. 1 is a crystal structure of ZIF-67;
FIG. 2 is an SEM photograph of a continuous ZIF-67 film of example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a continuous ZIF-67 membrane material, which comprises the following steps:
A) calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 membrane material through a formula (1);
Figure BDA0003308859690000041
in the formula (1), σmolarMaleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials2；
BET is the specific surface area of the polymeric substrate material, m2/g；
Rho is the mass areal density of the polymer substrate material, g/cm2；
A is an Avogastron constant;
a is the spacing, nm, between adjacent maleic anhydrides;
B) according to the calculation result of the step A), maleic anhydride is grafted 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;
C) mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a continuous ZIF-67 membrane material;
the metal salt is cobalt salt;
the solvent comprises methanol or water.
The invention firstly obtains the maleic anhydride grafting surface density required by the continuous ZIF-67 membrane material by calculation according to a formula (1).
In the present invention, a (nm) is defined as the distance between adjacent MAH (maleic anhydride) (i.e., the distance between nucleation points), and the microscopic density of MAH is 1/a2(group/nm-2) Wherein 1 represents on a surface a2Contains a nucleation point for the MOF crystal, which is contributed by MAH at the four corners (MAH at each corner is only 1/4).
Micro Density to MAH (σ)surfaceGeometric areal density) as shown in equation (2):
Figure BDA0003308859690000051
in the formula (2), A is an Avogastron constant (6.02X 10)23)；
nMAHIs the molar amount of grafted MAH (determined by titration);
Ssurfaceis the microscopic geometric area of the polymer substrate material.
Graft areal density (σ)molarMolar areal density) was calculated as in equation (3):
σmolar＝nMAH/Smolar (3)；
in the formula (3), SmolarIs the macroscopic double-sided area of the polymer substrate, and the two areas are converted, as shown in formula (4):
Ssurface＝Smolar×BET×ρ/2 (4)；
in the formula (4), BET is the specific surface area of the polymer base material, and m2(ii)/g; rho is the mass areal density of the polymer substrate material, g/cm2。
Geometric areal density (σ) of MAHsurface) And molar areal density (. sigma.)molar) The conversion is performed to obtain the conversion relationship between the two, as shown in formula (5):
Figure BDA0003308859690000052
in equation (5), a conversion relationship between the nucleation point spacing and the graft areal density (molar areal density) is established, as shown in equation (1):
Figure BDA0003308859690000053
in the formula (1), σmolarMaleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials2；
BET is the specific surface area of the polymeric substrate material, m2/g；
Rho is the mass areal density of the polymer substrate material, g/cm2；
A is an Avogastron constant;
a is the spacing, nm, of adjacent maleic anhydrides.
When the distance a between nucleation points is between the distances of two adjacent points in the MOF lattice (i.e., between the shortest distance and the longest distance), the corresponding maleic anhydride grafted areal density is a requirement for the formation of a continuous MOF film.
In certain embodiments of the present invention, the spacing a between adjacent maleic anhydrides is from 0.85 to 1.9 nm.
In certain embodiments of the present invention, the polymeric base material has a mass areal density ρ of 0.012g/cm2。
In certain embodiments of the invention, the polymeric substrate material has a specific surface area BET of 10.16m2/g。
In certain embodiments of the present invention, the maleic anhydride grafted areal density, σ, required for the continuous ZIF-67 membrane materialmolarIs 28 to 93.7nmol/cm2。
According to the calculation result, maleic anhydride is grafted on the surface of the high molecular base material by adopting a co-irradiation grafting method. In some embodiments of the present invention, grafting maleic anhydride onto the surface of a polymeric substrate material using a co-irradiation grafting method comprises:
in a sealed container, the tetrahydrofuran solution of maleic anhydride is immersed in the polymer substrate material, and after sealing, the polymer substrate material is put into a radiation source for carrying out co-radiation grafting.
In some embodiments of the present invention, the method further comprises, before immersing the solution of maleic anhydride in the polymeric substrate material:
and ultrasonically cleaning the polymer substrate material by using acetone, and drying.
The process parameters of the ultrasonic cleaning are not particularly limited in the present invention, and those of the ultrasonic cleaning known to those skilled in the art can be used.
In certain embodiments of the present invention, the temperature of the drying is 55 to 65 ℃.
In certain embodiments of the invention, the sealed container is an aluminum foil pouch.
In certain embodiments of the present invention, the concentration of the tetrahydrofuran solution of maleic anhydride is 1.0-1.5 g/mL. In certain embodiments, the concentration of the solution of maleic anhydride in tetrahydrofuran is 1.5 g/mL.
In some embodiments of the present invention, the polymer substrate material is a polymer nonwoven fabric or a polymer porous film. The material of the high polymer substrate material comprises at least one of UHMWPE, PP, PET, PTEF and PI. The thickness of the polymer base material is 0.42 mm.
In certain embodiments of the present invention, the radiation source for co-irradiation grafting comprises a cobalt 60 source or an electron accelerator, the radiation dose for co-irradiation grafting is 5-100 kGy, and the radiation dose rate is 0.3-5 kGy/h. In certain embodiments, the radiation dose for the co-irradiation grafting is 20kGy and 25 kGy. In certain embodiments, the radiation dose rate of the co-irradiation grafts is 2.7kGy/h and 600 Gy/h.
In certain embodiments of the present invention, the co-irradiation grafting is performed at room temperature.
In certain embodiments of the present invention, the co-irradiation grafting further comprises: ultrasonic cleaning and drying. And the ultrasonic cleaning is sequentially carried out by adopting tetrahydrofuran and ethanol. The process parameters of the ultrasonic cleaning are not particularly limited in the present invention, and those of the ultrasonic cleaning known to those skilled in the art can be used. The drying temperature is 55-65 ℃.
In certain 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 completed is 29.88nmol/cm2And 52.4nmol/cm2。
After the co-irradiation grafting is finished, growing a ZIF-67 layer in situ on the surface of the high polymer substrate material grafted with the maleic anhydride to obtain the continuous ZIF-67 film.
Specifically, the in-situ growth of the ZIF-8 layer on the surface of the maleic anhydride grafted polymer substrate material comprises the following steps:
and mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain the continuous ZIF-67 film.
Preferably, the method comprises the following steps:
dissolving a metal salt in a partial solvent to obtain a first solution;
dissolving the organic ligand in the residual solvent to obtain a second solution;
and after uniformly mixing the first solution and the second solution, putting the maleic anhydride grafted polymer substrate material into the uniformly mixed solution, and reacting to obtain the continuous ZIF-67 membrane.
In the present invention, the metal salt is a cobalt salt, and specifically may be Co (NO)3)2·6H2O。
In certain embodiments of the invention, the organic ligand has the structure of formula i;
Figure BDA0003308859690000071
in formula I, X is selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, vinyl or ester group.
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 present invention, the molar ratio of the metal salt to the organic ligand is 1 to 5: 1 to 1.2. In certain embodiments, the molar ratio of metal salt to organic ligand is 1.2: 1 or 1: 1.
in some embodiments of the present invention, the metal salt and the partial solvent are used in a ratio of 0.01 to 0.05 mol: 50 mL. In certain embodiments, the metal salt and the partial solvent are used in a ratio of 0.012 mol: 50mL or 0.01 mol: 50 mL.
In certain embodiments of the present invention, the ratio of the organic ligand to the residual solvent is 0.005 to 0.015 mol: 50-200 mL. In certain embodiments, the organic ligand and residual solvent are used in a ratio of 0.01 mol: 200 mL.
In the invention, the mixed solution obtained by uniformly mixing the first solution and the second solution can be used for immersing the polymer substrate material grafted with maleic anhydride, and the corresponding dosage and proportion are not specially limited.
In certain embodiments of the invention, the temperature of the reaction is 25 ℃.
In certain embodiments of the invention, the pressure of the reaction is 1 to 1.5 atm. In certain embodiments, the pressure of the reaction is 1 atm.
In some embodiments of the present invention, the reaction time is 12-36 h. In certain embodiments, the reaction time is 24 hours.
In certain embodiments of the present invention, after the reacting, further comprising: and (4) cleaning and drying. The cleaning is carried out by methanol. The drying temperature is 55-65 ℃.
After the co-irradiation grafting is finished, the ZIF-67 layer directly grows in situ on the surface of the high polymer substrate material grafted with the maleic anhydride, and an intermediate layer such as a molecular sieve intermediate layer or a zinc oxide coating does not need to be additionally introduced.
In the invention, maleic anhydride is directly grafted on the surface of a polymer base material by adopting a co-radiation grafting method, the maleic anhydride can form a covalent bond with the polymer base material, and the ZIF-67 grows by taking the maleic anhydride as a nucleation point, so that the ZIF-67 film can be firmly combined with the surface of a base material.
According to the preparation method of the continuous ZIF-67 membrane material, high-temperature roasting is not needed (>300 ℃), the preparation condition is mild, and the preparation method is suitable for various polymer substrates.
The continuous ZIF-67 membrane material prepared by the method disclosed by the invention is excellent in uranium adsorption capacity and selectivity. And a ZIF-67 layer directly grows on the surface of the high polymer substrate material grafted with the 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 for the ZIF-67 layer with the nanometer thickness without influencing 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 above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The invention also provides a continuous ZIF-67 membrane material prepared by the preparation method. The film prepared by the preparation method is a continuous defect-free film, the aperture of ZIF-67 is the only channel for the uranyl ions to pass through, so that the uranyl ions are removed by separating the uranyl ions, imidazole groups and cobalt affinity to the uranyl ions based on the ZIF-67 size effect, and the uranyl ions and imidazole groups have a synergistic effect and have good removal performance on the uranyl ions. Therefore, the continuous ZIF-67 film material prepared by the method has better uranium adsorption performance. Experimental results show that the continuous ZIF-67 membrane material provided by the invention can remove more than 95.1% of uranium in the solution by 2 times of circulating filtration under an extremely low uranium concentration (less than or equal to 3.3 ppb). The continuous ZIF-67 film material for extracting uranium from ultrafast seawater provided by the invention has good application prospect.
In order to further illustrate the present invention, a continuous ZIF-67 membrane material and a method for preparing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The reagents used in the following examples are all commercially available.
Example 1
The surface maleic anhydride graft areal density was calculated as follows:
the crystal structure of ZIF-67 is shown in FIG. 1, and FIG. 1 shows the crystal structure of ZIF-67. In the ZIF-67 crystal lattice, the distance between adjacent metals comprises three distances of 1, 2 and 3, the length range of the distance of 1-3 is 0.85-1.9 nm, and because zinc ions need to be coordinated with maleic anhydride, nucleation points of the ZIF-67 on the surface of the non-woven fabric are formed, so that a continuous film further grows, the distance a between the nucleation points, namely the distance between the maleic anhydride, and when a is 0.85-1.9 nm, the continuous film can be formed on the surface. In this example, the BET specific surface area of the nonwoven fabric was 10.16m2The mass surface density rho is 0.012g/cm2The Avgalois constant A is 6.02X 1023. According to the formula (1), the maleic anhydride grafting surface density sigma is calculatedmolarIs 28 to 93.7nmol/cm2. Therefore, when the surface maleic anhydride grafting area density range is 28-93.7 nmol/cm2In this case, a continuous ZIF-67 film can be grown in situ on the surface.
Example 2
Polypropylene (PP) nonwoven fabric with a thickness of 0.42mm was ultrasonically cleaned in acetone, dried at 60 ℃, and packed in an aluminum foil bag. Preparing a tetrahydrofuran solution of maleic anhydride with the mass fraction of 1.5g/mL, then adding the tetrahydrofuran solution of maleic anhydride and a polypropylene non-woven fabric into an aluminum foil bag, completely immersing the polypropylene non-woven fabric in the maleic anhydride solution, carrying out thermoplastic sealing on 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 2.7kGy/h, and the radiation dose is 20 kGy. Ultrasonic cleaning the irradiated polypropylene non-woven fabric with tetrahydrofuran and ethanol solvent in sequence, and drying at 60 ℃ to obtain the polypropylene non-woven fabric grafted with maleic anhydride, wherein the maleic anhydride grafted surface density is 29.88nmol/cm2。
Example 3
Mixing Co (NO)3)2·6H2O (3.49g, 0.012mol) was dissolved in 50mL of methanol to give a first solution; 2-methylimidazole (0.82g, 0.010mol) was dissolved in 200mL of methanol to obtain a second solution; after the first solution and the second solution were mixed, 4 pieces of the maleic anhydride-grafted polypropylene nonwoven fabric prepared in example 1 (monolithic area 50 function)200mm2) Immersing into the uniformly mixed solution, reacting for 24h in a reaction kettle at 25 ℃ and 1atm, cleaning the non-woven fabric membrane with methanol after the reaction is finished, and drying at 60 ℃ to obtain the continuous ZIF-67 membrane (CF-1).
The results of scanning electron microscopy analysis of the continuous ZIF-67 film (CF-1) obtained in example 3 are shown in FIG. 2. FIG. 2 is an SEM photograph of a continuous ZIF-67 film of example 3 of the present invention. As can be seen from FIG. 2, the surface of the non-woven fabric was densely grown with ZIF-67 particles, and the CF-1 film was continuously free of defects.
Example 4
Polypropylene (PP) nonwoven fabric with a thickness of 0.42mm was ultrasonically cleaned in acetone, dried at 60 ℃, and packed in an aluminum foil bag. Preparing a tetrahydrofuran solution of maleic anhydride with the mass fraction of 1.5g/mL, then adding the tetrahydrofuran solution of maleic anhydride and a polypropylene non-woven fabric into an aluminum foil bag, completely immersing the polypropylene non-woven fabric in the maleic anhydride solution, carrying out thermoplastic sealing on 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 25 kGy. Ultrasonic cleaning the irradiated polypropylene non-woven fabric with tetrahydrofuran and ethanol solvent in sequence, and drying at 60 ℃ to obtain the polypropylene non-woven fabric grafted with maleic anhydride, wherein the maleic anhydride grafted surface density is 52.4nmol/cm2。
Example 5
Mixing Co (NO)3)2·6H2O (2.98g, 0.010mol) was dissolved in 50mL of methanol to obtain a first solution; 2-methylimidazole (0.82g, 0.010mol) was dissolved in 200mL of methanol to obtain a second solution; after the first solution and the second solution were mixed well, 4 sheets of the maleic anhydride-grafted polypropylene nonwoven fabric (single sheet area 50X 200 mm) prepared in example 1 were attached2) Immersing into the uniformly mixed solution, reacting for 24h in a reaction kettle at 25 ℃ and 1atm, cleaning the non-woven fabric membrane with methanol after the reaction is finished, and drying at 60 ℃ to obtain the continuous ZIF-67 membrane (CF-2).
Example 6
The uranium adsorption performance of the prepared continuous ZIF-67 film (CF-1) was studied: a3.3 ppb uranium solution (the concentration of which is consistent with that of uranium in seawater) was filtered through a continuous ZIF-67 membrane (CF-1), the CF-1 membrane was cut into 35 mm-diameter round pieces, three pieces were taken and placed in a filter, and the time for filtering 1L uranium solution was 20 min. After filtering for 2 times, detecting the uranium concentration in the filtrate by using ICP-MS, and displaying the result that the clearance rate of uranium adsorption membranes to uranium in the solution reaches more than 97.2% through normal pressure filtration, thereby displaying excellent uranium adsorption performance.
Example 7
The uranium adsorption performance of the prepared continuous ZIF-67 film (CF-2) was studied: a3.3 ppb uranium solution (having a concentration corresponding to that of uranium in seawater) was filtered through a continuous ZIF-67 membrane (CF-2). the CF-2 membrane was cut into 35 mm-diameter circular pieces, three pieces were placed in a filter, and the time for filtering 1L uranium solution was 20 min. After filtering for 2 times, detecting the uranium concentration in the filtrate by using ICP-MS, and displaying the result that the clearance rate of uranium adsorption membranes to uranium in the solution reaches more than 95.1% through normal pressure filtration, thereby displaying excellent uranium adsorption performance.
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 (8)

1. A preparation method of a continuous ZIF-67 membrane material comprises the following steps:
A) calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 membrane material through a formula (1);
Figure FDA0003308859680000011
in the formula (1), σmolarMaleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials2；
BET is the specific surface area of the polymeric substrate material, m2/g；
Rho is the mass areal density of the polymer substrate material, g/cm2；
A is an Avogastron constant;
a is the spacing, nm, between adjacent maleic anhydrides;
B) according to the calculation result of the step A), maleic anhydride is grafted 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;
C) mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a continuous ZIF-67 membrane material;
the metal salt is cobalt salt;
the solvent comprises methanol or water.
2. The method according to claim 1, wherein the polymer base material is a polymer nonwoven fabric or a polymer porous film;
the material of the high polymer substrate material comprises at least one of UHMWPE, PP, PET, PTEF and PI.
3. The method of claim 1, wherein the co-irradiation 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-irradiation grafting is carried out at room temperature.
4. The method of claim 1, wherein grafting maleic anhydride onto the surface of the polymeric substrate material by using a co-irradiation grafting method comprises:
in a sealed container, the tetrahydrofuran solution of maleic anhydride is immersed in the polymer substrate material, and after sealing, the polymer substrate material is put into a radiation source for carrying out co-radiation grafting.
5. The preparation method of claim 1, wherein the organic ligand has a structure represented by formula i;
Figure FDA0003308859680000021
in formula I, X is selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, vinyl or ester group.
6. The preparation method according to claim 1, wherein the molar ratio of the metal salt to the organic ligand is 1-5: 1 to 1.2.
7. The method according to claim 1, wherein the reaction is carried out under a pressure of 1 to 1.5atm for 6 to 48 hours.
8. A continuous ZIF-67 membrane material prepared by the preparation method of any one of claims 1 to 7.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104959044A (en) * 2015-06-30 2015-10-07 浙江工业大学 Method for synthesizing metal organic framework film
CN106519281A (en) * 2016-11-09 2017-03-22 中国科学院长春应用化学研究所 Metal-organic framework composite and production method thereof
CN108912376A (en) * 2018-06-15 2018-11-30 中国科学院长春应用化学研究所 A kind of surface anti-ice material and preparation method thereof
WO2019210159A1 (en) * 2018-04-26 2019-10-31 Texas A&M University In situ fabrication of metal-organic framework films and mixed-matrix membranes
CN110560003A (en) * 2019-09-17 2019-12-13 北京理工大学 Core-shell structure Fe3O4@ ZIF-67 material, preparation and application thereof
US20200269194A1 (en) * 2019-02-26 2020-08-27 King Fahd University Of Petroleum And Minerals Porous membrane containing metal-organic frameworks

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104959044A (en) * 2015-06-30 2015-10-07 浙江工业大学 Method for synthesizing metal organic framework film
CN106519281A (en) * 2016-11-09 2017-03-22 中国科学院长春应用化学研究所 Metal-organic framework composite and production method thereof
WO2019210159A1 (en) * 2018-04-26 2019-10-31 Texas A&M University In situ fabrication of metal-organic framework films and mixed-matrix membranes
CN108912376A (en) * 2018-06-15 2018-11-30 中国科学院长春应用化学研究所 A kind of surface anti-ice material and preparation method thereof
US20200269194A1 (en) * 2019-02-26 2020-08-27 King Fahd University Of Petroleum And Minerals Porous membrane containing metal-organic frameworks
CN110560003A (en) * 2019-09-17 2019-12-13 北京理工大学 Core-shell structure Fe3O4@ ZIF-67 material, preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高健等: "高分子基底上大尺寸纳米厚度连续MOF膜的制备及其对于重金属清除的研究", 《中国核科学技术进展报告》, vol. 6, pages 30 - 33 *

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