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Modification method for effectively improving MOFs water stability and ammonia gas adsorption performance

A technology of water stability and adsorption performance, applied in chemical instruments and methods, separation methods, gas treatment, etc., can solve the problems of water stability hindering HKUST-1, crystal structure damage, skeleton collapse, etc.

Active Publication Date: 2019-11-19
BEIJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Although MOFs have many advantages, some are easy to absorb water and cause the collapse of the skeleton, such as HKUST-1, resulting in the destruction of the crystal structure
Therefore, its water stability has always been the bottleneck hindering the application of HKUST-1 in the environmental field.

Method used

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  • Modification method for effectively improving MOFs water stability and ammonia gas adsorption performance
  • Modification method for effectively improving MOFs water stability and ammonia gas adsorption performance
  • Modification method for effectively improving MOFs water stability and ammonia gas adsorption performance

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Weigh 0.135g of HKUST-1 granules, place in a 50mL three-neck flask, add 0.359g (3.45mmol) styrene and 0.162g (1.88mmol) methacrylic acid mixed monomer solution, then add 4mL dissolved in 0.02g (0.12mmol) azobisisobutyronitrile in tetrahydrofuran, placed at room temperature and magnetically stirred for 18-24h. After the stirring is completed, put it into an oil bath at 60-70°C to react for 6-8 hours. After the reaction stopped, centrifuge and remove the supernatant. The obtained solid was washed three times with 2-6 ml of tetrahydrofuran and acetone respectively, and the supernatant was removed by centrifugation each time. The cleaned product was left to dry naturally at room temperature, and after being fully dried, it was moved into a vacuum drying oven at 50°C for 24 hours. Finally, the composite material of (polystyrene-co-polymethacrylic acid) / HKUST-1 was obtained.

[0025] Weigh 0.1g of the composite material, put it into a glass tube with an inner diameter of 0...

Embodiment 2

[0027] Weigh 0.135g of HKUST-1 granules, place in a 50mL three-neck flask, add 0.359g (3.45mmol) styrene and 0.184g (1.88mmol) maleic anhydride mixed monomer solution, then add 4mL dissolved in 0.02g (0.12mmol) azobisisobutyronitrile in tetrahydrofuran, placed at room temperature and magnetically stirred for 18-24h. After the stirring is completed, put it into an oil bath at 60-70°C to react for 6-8 hours. After the reaction stopped, centrifuge and remove the supernatant. The obtained solid was washed three times with 2-6 ml of tetrahydrofuran and acetone respectively, and the supernatant was removed by centrifugation each time. The cleaned product was left to dry naturally at room temperature, and after being fully dried, it was moved into a vacuum drying oven at 50°C for 24 hours. Finally, a composite material of polystyrene-co-polymaleic anhydride) / HKUST-1 was obtained.

[0028] Weigh 0.1g of the composite material, put it into a glass tube with an inner diameter of 0.5c...

Embodiment 3

[0030] Weigh 0.135g of HKUST-1 granules, place them in a 50mL three-neck flask, add 0.555g (5.34mmol) of styrene monomer solution, and then add 4mL of tetrahydrofuran dissolved in 0.02g (0.12mmol) of azobisisobutyronitrile , placed under magnetic stirring at room temperature for 18-24h. After the stirring is completed, put it into an oil bath at 60-70°C to react for 6-8 hours. After the reaction stopped, centrifuge and remove the supernatant. The obtained solid was washed three times with 2-6 ml of tetrahydrofuran and acetone respectively, and the supernatant was removed by centrifugation each time. The cleaned product was left to dry naturally at room temperature, and after being fully dried, it was moved into a vacuum drying oven at 50°C for 24 hours. Finally, a composite material of polystyrene / HKUST-1 was obtained.

[0031] Weigh 0.1g of the composite material, put it into a glass tube with an inner diameter of 0.5cm, heat it at 120°C for 12h under the condition of a ni...

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Abstract

The invention discloses a modification method for effectively improving MOFs water stability, and belongs to the technical field of organic-inorganic porous composite materials. The method concretelyrelates to the use of a metal organic skeletal material MOFs as an inorganic phase and the use of a high specific surface and an internal pore structure of the MOFs. Monomers of an organic phase, suchas styrene, methacrylic acid and other olefin monomers, are introduced into the pore structure of the MOFs, and the monomers are induced to undergo free radical copolymerization in pores of a metal organic framework, thereby modifying a skeleton of the MOFs and improving the water stability. The free radical copolymerization is simple in reaction conditions and easy in implement. When the methodis applied to post-synthesis modification of the MOFs, the structure is not destroyed, and the water stability of the MOFs is improved. The MOFs has the absorption performance of ammonia, can be regenerated at high temperature to a certain extent, and can ensure the stability of a composite material in ammonia adsorption penetration.

Description

technical field [0001] The invention enhances the water stability of metal-organic framework materials through in-situ free radical copolymerization, and the composite material obtained after copolymerization in harmful gases such as ammonia gas, belongs to the technical field of organic-inorganic porous composite materials. Background technique [0002] Metal-organic frameworks (Metal-Organic Frameworks, MOFs) have the characteristics of ultra-high specific surface area, controllable pore size and adjustable chemical environment, and can be used in air purification, water environment treatment, gas storage and chemical sensing, etc. It shows a very good application prospect. As a typical MOFs material, HKUST-1 is formed by coordination self-assembly of copper salt and trimesic acid. Its crystal structure is similar to a paddle wheel, and each Cu ion is axially combined with a water molecule, which is easy to be removed to obtain a vacant metal active site, so that it exhib...

Claims

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Application Information

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IPC IPC(8): C08F292/00C08F212/08C08F220/06C08F222/06B01J20/22B01J20/30B01D53/02
CPCC08F292/00B01J20/226B01J20/261B01D53/02B01D2253/204B01D2257/406C08F212/08
Inventor 赵敏坚王思南王彬谢林华李建荣
Owner BEIJING UNIV OF TECH
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