CN113813923B - Continuous ZIF-8 membrane material and preparation method thereof - Google Patents
Continuous ZIF-8 membrane material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of membrane materials, in particular to a continuous ZIF-8 membrane material and a preparation method thereof. The invention provides a preparation method of a continuous ZIF-8 membrane material, which comprises the following steps: a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-8 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 to obtain a continuous ZIF-8 film material; the metal salt is zinc salt. 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
Technical Field
The invention relates to the technical field of membrane materials, in particular to a continuous ZIF-8 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 the advantage of good physicochemical stability. Currently, many countries have studied such adsorbent materials. Hydroxylamine treatment of polyacrylonitrile beads, such as Egawa, with hydroxylamine resulted in an amidoxime-functionalized polymeric adsorbent which achieved 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 the problem of slow adsorption speed at present, so that the time and cost for extracting uranium are greatly increased, 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-8 membrane material and a preparation method thereof, and the prepared continuous ZIF-8 membrane material has excellent uranium adsorption performance.
The invention provides a preparation method of a continuous ZIF-8 film material, which comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-8 membrane material through a formula (1);
in the formula (1), σ molar Maleic anhydride graft areal density, nmol/cm, required for continuous ZIF-8 film materials 2 ;
BET is the specific surface area of the polymeric substrate material, m 2 /g;
Rho is the mass areal density of the polymer substrate material, g/cm 2 ;
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 to obtain a continuous ZIF-8 membrane material;
the metal salt is zinc salt.
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;
in the formula I, X is selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, vinyl or ester group;
the solvent includes DMF, THF, or dioxane.
Preferably, the molar ratio of the metal salt to the organic ligand is 1:1.2 to 1.6.
Preferably, the ratio of the mass sum of the metal salt and the organic ligand to the amount of the solvent is 0.01 to 0.05g/mL.
Preferably, the reaction temperature is 100-150 ℃, the pressure is 1-3 atm, and the time is 12-36 h.
The invention also provides a continuous ZIF-8 membrane material prepared by the preparation method.
The invention provides a preparation method of a continuous ZIF-8 film material, which comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-8 membrane material through a formula (1);
in the formula (1), σ molar Maleic anhydride graft areal density, nmol/cm, required for continuous ZIF-8 film materials 2 ;
BET is the ratio of the polymeric substrate materialSurface area, m 2 /g;
Rho is the mass areal density of the polymer substrate material, g/cm 2 ;
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 the 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 to obtain a continuous ZIF-8 film material;
the metal salt is zinc salt.
The film prepared by the preparation method is a continuous defect-free film, the aperture of ZIF-8 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-8 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-8 film material prepared by the method has better uranium adsorption performance. Experimental results show that the continuous ZIF-8 membrane material provided by the invention can remove more than 96.5% of uranium in the solution through 2 times of circulating filtration under the condition of extremely low uranium concentration (less than or equal to 3.3 ppb). The continuous ZIF-8 film material for extracting uranium from ultrafast seawater has good application prospect.
Drawings
FIG. 1 is a crystal structure of ZIF-8;
FIG. 2 is an SEM photograph of a continuous ZIF-8 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-8 film material, which comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-8 membrane material through a formula (1);
in the formula (1), σ molar Maleic anhydride graft areal density, nmol/cm, required for continuous ZIF-8 film materials 2 ;
BET is the specific surface area of the polymeric substrate material, m 2 /g;
Rho is the mass areal density of the polymer substrate material, g/cm 2 ;
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 the 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 to obtain a continuous ZIF-8 membrane material;
the metal salt is zinc salt.
The invention firstly calculates the maleic anhydride grafting surface density required by the continuous ZIF-8 membrane material through a formula (1).
The present invention defines a (nm) as the spacing between adjacent MAHs (maleic anhydride) (i.e., the nucleation site spacing), and the microscopic density of MAHs is σ =1/a 2 (group/nm -2 ) Wherein 1 represents on a surface a 2 Contains a nucleation site for the MOF crystal, which is contributed by the MAH at the four corners (MAH at each corner is only 1/4).
Micro Density to MAH (σ) surface Geometric areal density) of the surfaceDerivation, as shown in equation (2):
in the formula (2), A is an Avogastron constant (6.02X 10) 23 );
n MAH Is the molar amount of grafted MAH (determined by titration);
S surface is the microscopic geometric area of the polymer substrate material.
Graft areal density (σ) molar Molar areal density) was calculated as in equation (3):
σ molar =n MAH /S molar (3);
in the formula (3), S molar Is the macroscopic double-sided area of the polymer substrate, and the two areas are converted, as shown in formula (4):
S surface =S molar ×BET×ρ/2 (4);
in the formula (4), BET is the specific surface area of the polymer base material, and m 2 (ii)/g; rho is the mass areal density of the polymer substrate material, g/cm 2 。
Again for geometric areal density (σ) of MAH surface ) And molar areal density (. Sigma.) molar ) The conversion is performed to obtain the conversion relationship between the two, as shown in formula (5):
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):
in the formula (1), σ molar The maleic anhydride grafting areal density required for the continuous ZIF-8 membrane material,nmol/cm 2 ;
BET is the specific surface area of the polymeric substrate material, m 2 /g;
Rho is the mass areal density of the polymer substrate material, g/cm 2 ;
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 invention, the spacing, a, between adjacent maleic anhydrides is from 0.85 to 1.9nm.
In certain embodiments of the present invention, the polymeric base material has a mass areal density ρ of 0.012g/cm 2 。
In certain embodiments of the invention, the polymeric substrate material has a specific surface area BET of 10.16m 2 /g。
In certain embodiments of the present invention, the maleic anhydride grafted areal density, σ, required for continuous ZIF-8 membrane materials molar Is 28 to 93.7nmol/cm 2 。
According to the calculation result, maleic anhydride is grafted on the surface of the polymer substrate material by adopting a co-irradiation grafting method, so that the polymer substrate material grafted with maleic anhydride is obtained. In the invention, the maleic anhydride grafting surface density obtained by adopting the co-irradiation grafting method is in the range of the maleic anhydride grafting surface density obtained by the calculation.
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 step of immersing the solution of maleic anhydride in tetrahydrofuran in the polymeric substrate material further comprises:
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 invention, the temperature of the drying is from 55 to 65 ℃.
In certain embodiments of the invention, the sealed container is an aluminum foil pouch.
In certain embodiments of the invention, the concentration of the solution of maleic anhydride in tetrahydrofuran is from 1.0 to 1.5g/mL. In certain embodiments, the concentration of the solution of maleic anhydride in tetrahydrofuran is 1.5g/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 base material comprises at least one of UHMWPE, PP, PET, PTEF and PI. The thickness of the polymer base material is 0.42mm.
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 25kGy. In certain embodiments, the radiation dose rate of the co-irradiation grafting is 2.7kGy/h and 600Gy/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/cm 2 Or 52.4nmol/cm 2 。
After the co-irradiation grafting is finished, growing a ZIF-8 layer on the surface of the high polymer substrate material grafted with maleic anhydride in situ to obtain a continuous ZIF-8 film material.
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 to obtain the continuous ZIF-8 membrane material.
Preferably, the method comprises the following steps: dissolving metal salt and organic ligand in a solvent, uniformly mixing, putting the maleic anhydride grafted polymer substrate material into the uniformly mixed solution, and reacting to obtain the continuous ZIF-8 membrane material.
In the present invention, the metal salt is a zinc salt, and specifically may be Zn (NO) 3 ) 2 ·6H 2 O。
In certain embodiments of the invention, the organic ligand has the structure of formula i;
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 DMF, THF, or dioxane.
In certain embodiments of the invention, the molar ratio of the metal salt to the organic ligand is 1:1.2 to 1.6. In certain embodiments, the metal salt and organic ligand are present in a molar ratio of 1:1.2.
in certain embodiments of the invention, the ratio of the sum of the mass of the metal salt and the organic ligand to the amount of the solvent is 0.01 to 0.05g/mL. In certain embodiments, the ratio of the sum of the mass of the metal salt and organic ligand to the amount of solvent used is 0.0155g/mL.
In the invention, the solution obtained by mixing the metal salt, the organic ligand and the solvent can be used for immersing the high-molecular substrate material grafted with the maleic anhydride.
In certain embodiments of the invention, the reaction is carried out at a temperature of 100 to 150 ℃ and a pressure of 1 to 3atm for a time of 12 to 36 hours. In certain embodiments, the temperature of the reaction is 140 ℃. In certain embodiments, the pressure of the reaction is 1.5atm. 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 washing is carried out by sequentially adopting N, N-Dimethylformamide (DMF) and chloroform. The drying temperature is 55-65 ℃.
After the co-irradiation grafting is finished, the ZIF-8 layer directly grows on the surface of the maleic anhydride grafted polymer substrate material in situ, 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 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-8 grows by taking the maleic anhydride as a nucleation point, so that the ZIF-8 film can be firmly combined with the surface of the base material.
According to the preparation method of the continuous ZIF-8 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-8 film material prepared by the method has better uranium adsorption capacity and selectivity. And a ZIF-8 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-8 layer with the nanometer thickness without influencing the flux of the ZIF-8 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 the raw materials may be those generally commercially available.
The invention also provides a continuous ZIF-8 membrane material prepared by the preparation method. The film prepared by the preparation method is a continuous defect-free film, the aperture of ZIF-8 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-8 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-8 film material prepared by the method has better uranium adsorption performance. Experimental results show that the continuous ZIF-8 membrane material provided by the invention can remove more than 96.5% of uranium in the solution through 2 times of circulating filtration under the condition of extremely low uranium concentration (less than or equal to 3.3 ppb). The continuous ZIF-8 film material for extracting uranium from ultrafast seawater has good application prospect.
In order to further illustrate the present invention, a continuous ZIF-8 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-8 is shown in FIG. 1, and FIG. 1 shows the crystal structure of ZIF-8. In the ZIF-8 crystal lattice, the distance between adjacent metals comprises 1,2,3, the length of the distance between 1 and 3 ranges from 0.85 to 1.9nm, and as zinc ions need to be coordinated with maleic anhydride to form a nucleation point of ZIF-8 on the surface of the non-woven fabric, the continuous film is further grown, so that the distance a between the nucleation points, namely the distance between the maleic anhydride, can form the continuous film on the surface when the a is 0.85 to 1.9nm. In this example, the BET specific surface area of the nonwoven fabric was 10.16m 2 The mass surface density rho is 0.012g/cm 2 The Avogastron constant A is 6.02 × 10 23 . According to the formula (1), the maleic anhydride grafting surface density sigma is calculated molar Is 28 to 93.7nmol/cm 2 . Therefore, when the surface maleic anhydride grafting surface density is in the range of 28-93.7 nmol/cm 2 When in use, the continuous ZIF-8 film can be grown on the surface in situ.
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 polypropylene non-woven fabric into an aluminum foil bag to enable the polypropylene non-woven fabric to be completely immersed in the maleic anhydride solution, sealing the aluminum foil bag by thermal molding, and placing the aluminum foil bag into a radiation source (an electron accelerator) to perform irradiation at room temperature, wherein the radiation dose rate is 2.7kGy/h, and the radiation dose is 20kGy. 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/cm 2 。
Example 3
Adding Zn (NO) 3 ) 2 ·6H 2 O (2.10 g, 0.007mol) and 2-methylimidazole (0.69g, 0.0084mol) were dissolved in 180mL of DMF, and 4 pieces of the maleic anhydride-grafted polypropylene nonwoven fabric (single-piece area 50X 200 mm) 2 ) Putting the mixture into the solution, reacting for 24 hours in a hydrothermal reaction kettle at 140 ℃ under 1.5atm, washing the non-woven fabric membrane by using DMF (dimethyl formamide) and chloroform in sequence after the reaction is finished, and drying at 60 ℃ to obtain the continuous ZIF-8 membrane (CZ-1).
The continuous ZIF-8 film (CZ-1) obtained in example 3 was analyzed by scanning electron microscopy, and the results are shown in FIG. 2. FIG. 2 is an SEM photograph of a continuous ZIF-8 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-8 particles, and the CZ-1 film was continuously free of defects.
Example 4
Polypropylene (PP) nonwoven fabrics with the thickness of 0.42mm are ultrasonically cleaned in acetone, dried at 60 ℃ and then packaged 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 600Gy/h, and the radiation dose is 25kGy. The irradiated polypropylene non-woven fabricUltrasonic cleaning with tetrahydrofuran and ethanol solvent in sequence, drying at 60 deg.C to obtain polypropylene nonwoven fabric grafted with maleic anhydride, wherein the maleic anhydride grafted surface density is 52.4nmol/cm 2 。
Example 5
Adding Zn (NO) 3 ) 2 ·6H 2 O (2.10 g, 0.007mol) and 2-methylimidazole (0.69g, 0.0084mol) were dissolved in 180mL of DMF, and 4 pieces of the maleic anhydride-grafted polypropylene nonwoven fabric (single-piece area 50X 200 mm) 2 ) Immersing the membrane into the solution, reacting for 24 hours in a hydrothermal reaction kettle at 140 ℃ under 1.5atm, sequentially washing the non-woven fabric membrane by using DMF and chloroform after the reaction is finished, and drying at 60 ℃ to obtain the continuous ZIF-8 membrane (CZ-2).
Example 6
The uranium adsorption performance of the prepared continuous ZIF-8 film (CZ-1) is researched: a3.3 ppb uranium solution (having a concentration corresponding to the concentration of uranium in seawater) was filtered through a continuous ZIF-8 membrane (CZ-1). Cutting the CZ-1 membrane into 35 mm-diameter circular sheets, placing three sheets in a filter, and filtering 1L uranium solution for 15min. 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% through normal pressure filtration, thereby displaying excellent uranium adsorption performance.
Example 7
The uranium adsorption performance of the prepared continuous ZIF-8 film (CZ-2) is researched: a 3.3ppb uranium solution (having a concentration corresponding to the concentration of uranium in seawater) was filtered through a continuous ZIF-8 membrane (CZ-2). Cutting the CZ-1 membrane into 35 mm-diameter circular sheets, placing three sheets in a filter, and filtering 1L uranium solution for 15min. After filtering for 2 times, detecting the uranium concentration in the filtrate by ICP-MS, and displaying the result that the clearance rate of uranium in the solution by the uranium adsorption film reaches more than 96.5% 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-8 membrane material comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-8 membrane material through a formula (1);
in the formula (1), σ molar Maleic anhydride grafted surface Density, nmol/cm, required for continuous ZIF-8 Membrane Material 2 ;
BET is the specific surface area of the polymeric substrate material, m 2 /g;
Rho is the mass surface density of the polymer substrate material, g/cm 2 ;
A is an Avogastron constant;
a is the spacing, nm, between adjacent maleic anhydrides; the distance between adjacent maleic anhydride is 0.85-1.9 nm;
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 the polymer substrate material grafted with maleic anhydride; the polymer substrate material is a polymer non-woven fabric or a polymer porous membrane;
c) Mixing metal salt, an organic ligand, a solvent and a high polymer substrate material grafted with maleic anhydride, and reacting to obtain a continuous ZIF-8 membrane material;
the metal salt is zinc salt; the organic ligand is 2-methylimidazole; the solvent is DMF.
2. The method according to claim 1, wherein the material of the 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 method according to claim 1, wherein the molar ratio of the metal salt to the organic ligand is 1:1.2 to 1.6.
6. The method according to claim 1, wherein the ratio of the sum of the mass of the metal salt and the organic ligand to the amount of the solvent is 0.01 to 0.05g/mL.
7. The method according to claim 1, wherein the reaction temperature is 100 to 150 ℃, the pressure is 1 to 3atm, and the reaction time is 12 to 36 hours.
8. A continuous ZIF-8 film material prepared by the preparation method of any one of claims 1 to 7.
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