CN113813925B - Continuous ZIF-67 film material and preparation method thereof - Google Patents
Continuous ZIF-67 film material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 48
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 34
- -1 uranyl ions Chemical class 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004364 calculation method Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 230000005855 radiation Effects 0.000 claims description 21
- 239000004745 nonwoven fabric Substances 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 4
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 3
- 230000005476 size effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 34
- 238000001035 drying Methods 0.000 description 10
- 239000013535 sea water Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 239000012923 MOF film Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- 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]
-
- 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
-
- 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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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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- 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
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- Separation Using Semi-Permeable Membranes (AREA)
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 film material comprises the following steps: a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 film material through a formula (1); b) Grafting maleic anhydride on the surface of the high polymer substrate material by adopting a co-radiation grafting method according to the calculation result of the step A) to obtain a high polymer substrate material grafted with maleic anhydride; c) 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 continuous ZIF-8 film material; the metal salt is cobalt salt; the solvent comprises methanol or water. The invention prepares a continuous defect-free membrane, and the removal of uranyl ions is based on ZIF-8 size effect to separate the affinity of uranyl ions and imidazole groups to uranyl ions, and the two have synergistic effect and better uranium adsorption performance.
Description
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 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 continuous ZIF-67 film material and a preparation method thereof, and the continuous ZIF-67 film material prepared by the invention has better uranium adsorption performance.
The invention provides a preparation method of a continuous ZIF-67 film material, which comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 film material through a formula (1);
in the formula (1), sigma molar Maleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials 2 ；
BET is the specific surface area, m, of the polymeric substrate material 2 /g；
ρ is the mass areal density, g/cm, of the polymeric substrate material 2 ；
A is an avogalileo constant;
a is the spacing of adjacent maleic anhydride, nm;
b) Grafting maleic anhydride on the surface of the high polymer substrate material by adopting a co-radiation grafting method according to the calculation result of the step A) to obtain a high polymer substrate material grafted with maleic anhydride;
c) 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 continuous ZIF-67 film material;
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 put into a radiation source after being soaked by a polymer base material and sealed, and co-radiation grafting is carried out.
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 1-5: 1 to 1.2.
Preferably, the pressure of the reaction is 1 to 1.5atm for 6 to 48 hours.
The invention also provides a continuous ZIF-67 film material prepared by the preparation method.
The invention provides a preparation method of a continuous ZIF-67 film material, which comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 film material through a formula (1);
in the formula (1), sigma molar Maleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials 2 ；
BET is the specific surface area, m, of the polymeric substrate material 2 /g；
ρ is the mass areal density, g/cm, of the polymeric substrate material 2 ；
A is an avogalileo constant;
a is the spacing of adjacent maleic anhydride, nm;
b) Grafting maleic anhydride on the surface of the high polymer substrate material by adopting a co-radiation grafting method according to the calculation result of the step A) to obtain a high polymer substrate material grafted with maleic anhydride;
c) 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 continuous ZIF-67 film material;
the metal salt is cobalt salt;
the solvent includes methanol or water.
The preparation method provided by the invention is used for preparing the continuous defect-free membrane, the aperture of the ZIF-67 is the only channel for the passage of uranyl ions, so that the removal of the uranyl ions is realized by separating the affinities of the uranyl ions and imidazole groups to the uranyl ions based on the ZIF-67 size effect, and the two have synergistic effect, thus achieving good removal performance for the uranyl ions. Therefore, the continuous ZIF-67 film material prepared by the invention has better uranium adsorption performance. Experimental results show that the continuous ZIF-67 film material provided by the invention can remove over 95.1% of uranium in the solution through 2 times of circulating filtration under extremely low uranium concentration (less than or equal to 3.3 ppb). Not only realizes the rapid high-selectivity uranium extraction, but also the membrane material is easy to recycle and post-treat and has good durability, so the continuous ZIF-67 membrane material for the ultra-rapid uranium extraction of seawater has good application prospect.
Drawings
FIG. 1 is a crystal structure of ZIF-67;
FIG. 2 is an SEM image of a continuous ZIF-67 film of example 3 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 continuous ZIF-67 film material, which comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 film material through a formula (1);
in the formula (1), sigma molar Maleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials 2 ；
BET is the specific surface area, m, of the polymeric substrate material 2 /g；
ρ is the mass areal density, g/cm, of the polymeric substrate material 2 ；
A is an avogalileo constant;
a is the spacing of adjacent maleic anhydride, nm;
b) Grafting maleic anhydride on the surface of the high polymer substrate material by adopting a co-radiation grafting method according to the calculation result of the step A) to obtain a high polymer substrate material grafted with maleic anhydride;
c) 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 continuous ZIF-67 film material;
the metal salt is cobalt salt;
the solvent includes methanol or water.
The maleic anhydride grafting surface density required by the continuous ZIF-67 film material is calculated by the formula (1).
The invention defines a (nm) as the distance between adjacent MAH (maleic anhydride) (i.e. nucleation point distance), then the microscopic density of MAH is σ=1/a 2 (group/nm -2 ) Wherein 1 represents a surface a 2 Contains a MOF crystal nucleation site within the unit cell, which is contributed by MAH at the four corners (MAH at each corner is only 1/4).
Microscopic Density (Sigma) for MAH surface Geometric areal density) as shown in equation (2):
in the formula (2), A is an Avgalileo constant (6.02X10) 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.
Grafting areal Density (sigma) molar Molar areal density) is calculated as in equation (3):
σ molar ＝n MAH /S molar (3)；
in the formula (3), S molar The macro double-sided area of the polymer substrate is converted into two areas, as shown in a formula (4):
S surface ＝S molar ×BET×ρ/2 (4)；
in the formula (4), BET is the specific surface area, m of the polymer base material 2 /g; ρ is the mass areal density, g/cm, of the polymeric substrate material 2 。
And then to the geometric surface Density (sigma) of MAH surface ) And molar area density (sigma) molar ) And converting to obtain a conversion relationship between the two, as shown in a formula (5):
in the formula (5), a conversion relation between nucleation point spacing and grafting surface density (molar surface density) is established, as shown in the formula (1):
in the formula (1), sigma molar Maleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials 2 ；
BET is the specific surface area, m, of the polymeric substrate material 2 /g；
ρ is the mass areal density, g/cm, of the polymeric substrate material 2 ；
A is an avogalileo constant;
a is the spacing of adjacent maleic anhydride, nm.
When the distance a between nucleation sites is between the distances of two adjacent sites in the MOF lattice (i.e., between the shortest distance and the longest distance), the corresponding maleic anhydride grafting areal density is a necessary condition for forming a continuous MOF film.
In certain embodiments of the invention, the spacing a between adjacent maleic anhydride is 0.85 to 1.9nm.
In certain embodiments of the present invention, the polymeric substrate material has a mass areal density ρ of 0.012g/cm 2 。
In certain embodiments of the present invention, the polymeric base 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 sigma required for continuous ZIF-67 film materials molar 28 to 93.7nmol/cm 2 。
And grafting maleic anhydride on the surface of the high polymer substrate material by adopting a co-radiation grafting method according to the calculation result. 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 20kGy and 25kGy. In certain embodiments, the co-radiation grafted radiation dose rate is 2.7kGy/h and 600Gy/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 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 29.88nmol/cm 2 And 52.4nmol/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 continuous 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 continuous 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 to obtain the continuous 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 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 certain embodiments of the invention, the metal salt and the portion of solvent are used in an amount ratio of 0.01 to 0.05mol:50mL. In certain embodiments, the metal salt and the portion of solvent are used in an amount ratio of 0.012mol:50mL or 0.01mol:50mL.
In certain embodiments of the invention, the ratio of the organic ligand to the remaining solvent is from 0.005 to 0.015mol: 50-200 mL. In certain embodiments, the ratio of the organic ligand to the remaining solvent is 0.01mol:200mL.
In the invention, the mixed solution obtained by uniformly mixing the first solution and the second solution can submerge the polymer substrate material grafted with the maleic anhydride, and the corresponding dosage proportion is not particularly 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 1.5atm. In certain embodiments, the pressure of the reaction is 1atm.
In certain embodiments of the invention, the reaction time is 12 to 36 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.
In the preparation method of the continuous ZIF-67 film material provided by the invention, 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 continuous 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 continuous ZIF-67 film material prepared by the preparation method. The preparation method provided by the invention is used for preparing the continuous defect-free membrane, the aperture of the ZIF-67 is the only channel for the passage of uranyl ions, so that the removal of the uranyl ions is realized by separating the affinities of the uranyl ions, imidazole groups and cobalt to the uranyl ions based on the ZIF-67 size effect, and the two have synergistic effects, thereby achieving good removal performance of the uranyl ions. Therefore, the continuous ZIF-67 film material prepared by the invention has better uranium adsorption performance. Experimental results show that the continuous ZIF-67 film material provided by the invention can remove over 95.1% of uranium in the solution through 2 times of circulating filtration under extremely low uranium concentration (less than or equal to 3.3 ppb). Not only realizes the rapid high-selectivity uranium extraction, but also the membrane material is easy to recycle and post-treat and has good durability, so the continuous ZIF-67 membrane material for the ultra-rapid uranium extraction of seawater has good application prospect.
In order to further illustrate the present invention, the following examples are provided to illustrate a continuous ZIF-67 film material and a method for preparing the same, but should not be construed to limit the scope of the present invention.
The reagents used in the examples below 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 lattice, the distance between adjacent metals comprises three distances of 1,2 and 3, the length range of the distances of 1-3 is 0.85-1.9 nm, and zinc ions need to coordinate with maleic anhydride to form nucleation points of ZIF-67 on the surface of the non-woven fabric, so that the continuous film further grows, and the nucleation point distance a is the distance between maleic anhydride, and when a is 0.85-1.9 nm, the surface can form the continuous film. In this example, the BET specific surface area of the nonwoven fabric was 10.16m 2 Per gram, a mass areal density ρ of 0.012g/cm 2 The Avgalileo constant A is 6.02X10 23 . According to the formula (1), the maleic anhydride grafting surface density sigma is calculated molar 28 to 93.7nmol/cm 2 . Therefore, when the surface maleic anhydride grafting surface density interval is 28 to 93.7nmol/cm 2 When the surface is in situ grown, a continuous ZIF-67 film may be grown.
Example 2
A polypropylene (PP) nonwoven fabric of 0.42mm thickness was ultrasonically cleaned in acetone, dried at 60 ℃ and packed into 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 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 2.7kGy/h and the radiation dose is 20kGy. 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 29.88nmol/cm 2 。
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 ) Immersing the membrane into the uniformly mixed solution, reacting for 24 hours at 25 ℃ and 1atm in a reaction kettle, cleaning the non-woven fabric membrane by using methanol after the reaction is finished, and drying at 60 ℃ to obtain the continuous ZIF-67 membrane (CF-1).
The continuous ZIF-67 film (CF-1) obtained in example 3 was subjected to scanning electron microscopy and the results are shown in FIG. 2. FIG. 2 is an SEM image of a continuous ZIF-67 film of example 3 of the present invention. As can be seen from FIG. 2, the surface of the nonwoven fabric was densely packed with ZIF-67 particles, and the CF-1 film was continuously defect-free.
Example 4
A polypropylene (PP) nonwoven fabric of 0.42mm thickness was ultrasonically cleaned in acetone, dried at 60 ℃ and packed into an aluminum foil bag. A tetrahydrofuran solution of maleic anhydride was prepared at a mass fraction of 1.5g/mL, followed by maleic anhydrideThe tetrahydrofuran solution of the anhydride and the polypropylene non-woven fabric are added into an aluminum foil bag, so that the maleic anhydride solution completely submerges the polypropylene non-woven fabric, the aluminum foil bag is sealed in a thermoplastic mode, and the aluminum foil bag is placed into a radiation source (an electron accelerator) for irradiation at room temperature, wherein the radiation dosage rate is 0.6kGy/h, and the radiation dosage is 25kGy. 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 52.4nmol/cm 2 。
Example 5
Co (NO) 3 ) 2 ·6H 2 O (2.98 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 ) Immersing the membrane into the uniformly mixed solution, reacting for 24 hours at 25 ℃ and 1atm in a reaction kettle, cleaning a non-woven fabric membrane by using 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) is studied: 3.3ppb uranium solution (concentration consistent with that of uranium in seawater) was filtered with a continuous ZIF-67 membrane (CF-1), the CF-1 membrane was cut into 35mm diameter discs, three discs were taken and placed in the filter, and the 1L uranium solution was filtered for 20min. After 2 times of filtration, the concentration of uranium 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 97.2% through normal pressure filtration, and the excellent uranium adsorption performance is shown.
Example 7
The uranium adsorption performance of the prepared continuous ZIF-67 film (CF-2) is studied: filtering 3.3ppb uranium solution (concentration consistent with that of uranium in seawater) with continuous ZIF-67 film (CF-2), cutting CF-2 film into 35mm diameter discs, placing three discs in filter, and filtering 1L uranium solution for 20min. 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 95.1% 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 (6)
1. The preparation method of the continuous ZIF-67 membrane material for uranium adsorption comprises the following steps:
a) Calculating to obtain the maleic anhydride grafting surface density required by the continuous ZIF-67 film material through a formula (1);
（1）；
in the formula (1),σ molar maleic anhydride grafted areal density, nmol/cm, required for continuous ZIF-67 film materials 2 ；
BETIs the specific surface area, m of the polymer substrate material 2 /g；
ρIs the mass surface density, g/cm of the polymer substrate material 2 ；
AIs the avogalileo constant;
ais the spacing of adjacent maleic anhydride, nm; spacing of the adjacent maleic anhydridea0.85-1.9 nm;
b) Grafting maleic anhydride on the surface of the high polymer substrate material by adopting a co-radiation grafting method according to the calculation result of the step A) to obtain a high 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 polymer substrate material grafted with maleic anhydride, and reacting at 15-40 ℃ to obtain a continuous ZIF-67 membrane material for uranium adsorption;
the metal salt is cobalt salt; the organic ligand is 2-methylimidazole;
the solvent includes methanol or water.
2. The preparation method according to claim 1, wherein the polymer base material comprises at least one of ultra-high molecular weight polyethylene UHMWPE, polypropylene PP, polyethylene terephthalate PET, polytetrafluoroethylene PTEF and polyimide 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 put into a radiation source after being soaked by a polymer base material and sealed, and co-radiation grafting is carried out.
5. 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.
6. The method according to claim 1, wherein the pressure of the reaction is 1 to 1.5atm for 6 to 48 hours.
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