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Macro-size continuous MOF (Metal Organic Framework) membrane material as well as preparation method and application thereof

A membrane material, MOF technology, applied in chemical instruments and methods, other chemical processes, alkali metal oxides/hydroxides, etc.

Active Publication Date: 2021-12-31
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004]However, both the adsorption rate and the adsorption rate of the above materials need to be further improved

Method used

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  • Macro-size continuous MOF (Metal Organic Framework) membrane material as well as preparation method and application thereof
  • Macro-size continuous MOF (Metal Organic Framework) membrane material as well as preparation method and application thereof
  • Macro-size continuous MOF (Metal Organic Framework) membrane material as well as preparation method and application thereof

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preparation example Construction

[0033] The invention provides a method for preparing a macro-sized continuous MOF membrane material, comprising the following steps:

[0034] A) immersing the polymer base material in an organic solution of maleic anhydride, and performing irradiation treatment to obtain a polymer base grafted with maleic anhydride;

[0035] The molar surface density σ of the maleic anhydride of the polymer substrate grafted with maleic anhydride molar Satisfy the formula I relation:

[0036]

[0037] In formula I, a is the distance between adjacent nucleation points, and a is between two adjacent points in the MOF lattice; BET is the specific surface area of ​​the polymer substrate; ρ is the mass areal density of the polymer substrate; A is Avogadro's constant; σ molar is the molar surface density;

[0038] B) mixing the zirconium salt, the cyano-modified organic ligand and the polymer substrate grafted with maleic anhydride in the step A), and reacting to obtain a continuous MOF grafte...

Embodiment 1

[0091] ①Theoretical calculation

[0092] The lattice structure of UiO-66-AO is shown in the figure above, and when the distance between maleic anhydrides is 1.467nm-2.075nm, a continuous film can be formed on the surface. The BET specific surface area of ​​the polypropylene non-woven fabric used is 10.16m 2 / g, mass areal density is 0.012g / cm 2 . According to formula 1, the surface density of maleic anhydride grafted is calculated as 23.519~47.053nmol / cm 2 . Therefore, when the surface density range of maleic anhydride grafted surface is 23.519~47.053nmol / cm 2 , the continuous UiO-66-AO film can be grown in situ on the surface.

[0093] ② Modification of organic ligands

[0094] Dissolve 4mmol of 2-aminoterephthalic acid and 6mmol of sodium hydroxide in 50mL of water. Add 10 mmol of acrylonitrile and 0.1 mmol of hydroquinone to the solution, stir and dissolve, and react at 100 degrees Celsius for 12 hours. After the reaction is over, add 30% hydrochloric acid to the sy...

Embodiment 2

[0103] A 0.42 mm thick polypropylene non-woven fabric (PP) was ultrasonically cleaned in acetone, dried at 60°C and packed into an aluminum foil bag. It is 50% maleic anhydride / tetrahydrofuran solution that configuration mass fraction is at room temperature, then maleic anhydride solution and polypropylene non-woven fabric identical with embodiment 1 are added in the aluminum foil bag, make maleic anhydride solution immerse substrate completely, heat Plastic-seal the aluminum foil bag and place it in the radiation source for irradiation. The irradiation dose rate is 50Gy / min, and the absorbed dose is 10kGy. The irradiated polypropylene non-woven fabric was ultrasonically cleaned with tetrahydrofuran and ethanol solvents in sequence, and dried at 60°C to obtain a polypropylene non-woven fabric grafted with maleic anhydride. The graft surface density of maleic anhydride was 32.09 nmol / cm 2 .

[0104] ZrCl 4 and 2-cyanoterephthalic acid were added in DMF at a molar ratio of 1:...

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Abstract

The invention provides a preparation method of a macro-size continuous MOF (Metal Organic Framework) membrane material. According to the method, a maleic anhydride grafting surface density interval required for preparing a continuous MOF layer is theoretically calculated, and then maleic anhydride is grated on the surface of a microporous polymeric membrane by adopting a co-radiation grafting method. By changing the absorbed dose and the dose rate, the maleic anhydride grafting surface density on the surface of the polymeric membrane is regulated in a required range, and finally, a continuous MOF layer containing an amidoxime group grows in situ on the surface of the polymeric membrane grafted with maleic anhydride. A continuous UiO-66-AO film can fully play a role in screening and adsorption. The porous characteristic of continuous UiO-66-AO and the good coordination effect of high-density amidoxime groups on uranyl ions are utilized, the continuous UiO-66-AO and the high-density amidoxime groups cooperate to selectively adsorb uranium, the adsorption capacity and selectivity of uranium are greatly improved, and the uranium extraction speed is increased. The invention also provides the macro-size continuous MOF membrane material and application thereof.

Description

technical field [0001] The invention belongs to the technical field of organic polymer materials, and in particular relates to a macro-sized continuous MOF membrane material, its preparation method and application. Background technique [0002] In recent years, with the advancement of science and technology in human society and the rapid development of industry, energy consumption has increased day by day, leading to the increasingly scarce fossil fuel resources, and the excessive combustion of fossil fuels has also caused serious environmental problems such as the greenhouse effect and global warming. Solving energy shortages And environmental pollution has always been the theme of the times. As a new type of clean energy, nuclear energy is considered to be the best energy to replace fossil energy. Uranium is the most important dye in nuclear fission reactors, but the global exploitable ore uranium resources are very limited, only one thousandth of the uranium reserves in ...

Claims

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Application Information

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IPC IPC(8): B01J20/22B01J20/28B01J20/30D06M14/28D06M15/37C08G83/00C22B60/02C22B7/00
CPCB01J20/226B01J20/22B01J20/28033D06M14/28D06M15/37C08G83/008C22B60/0265C22B7/006Y02P10/20
Inventor 张依帆高健郑春柏柳美华魏巍邓鹏飏
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI