Micro-porous metal organic framework material for methane and acetylene adsorption and storage, and preparation method of micro-porous metal organic framework material

Abstract

The invention discloses a micro-porous metal organic framework material for methane and acetylene adsorption and storage, and a preparation method of the micro-porous metal organic framework material. The metal organic framework material is a three-dimensional crystal material prepared from self-assembling transition-metal ions and a polycarboxylic acid organic ligand 5,5',5''-(9H-carbazole-3,6,9-tri-yl)-m-phthalic acid by virtue of coordinate bonds. The metal organic framework material has the relatively large specific surface area and pore volume, the specific surface area can be 1200-1400m<2> / g, the pore volume is 0.6-0.8cm<3> / g, and the metal organic framework material is high in thermal stability and simple in preparation process. The material has high-density open metal sites, can increase the methane and acetylene adsorption and storage amount under 273K and 298K and can be expected to serve as a novel high-efficiency methane and acetylene adsorption and storage material.

Description

technical field

[0001] The invention relates to a microporous metal organic framework material and a preparation method thereof, in particular to a microporous metal organic framework material for methane and acetylene adsorption and storage and a preparation method thereof. Background technique

[0002] Methane is the main component of natural gas, and the C / H ratio of methane is very high. Compared with traditional energy sources such as petroleum, coal and other fossil fuels, methane is a clean fuel and environmentally friendly. At present, there are three main ways to store methane: liquefied methane, compressed methane and adsorbed methane. The liquefaction and compression method consumes a lot of energy and is complicated to operate, which has great potential safety hazards. The above problems prevent the liquefaction and compression of methane from being widely used. For commercial applications, traditional methane-absorbing materials include activated carbon and zeol...

Examples

Embodiment 1

[0030] (1) Dissolve 10g (50mmol) of 5-amino-isophthalic acid dimethyl ester into 225mL of hydrobromic acid solution with a mass concentration of 15%, stir and cool to 0°C, add dropwise 23mL of The aqueous solution of sodium nitrite of L carries out diazotization reaction, obtains diazonium salt solution;

[0031] (2) 9.8g cuprous bromide is dissolved in 90mL mass concentration and is in the hydrobromic acid solution of 15%, after being cooled to 0 ℃, in this solution, add dropwise the diazonium salt solution that step (1) obtains while stirring, React at 0°C for 30 minutes, and then react at room temperature for 12 hours. After the reaction, filter the organic layer and wash it repeatedly with water. Dissolve the organic layer in dichloromethane and wash with anhydrous MgSO 4 After drying and filtering, use petroleum ether and ethyl acetate (volume ratio 8:1) as the eluent to carry out column chromatography separation and purification to obtain 10.5 g of 5-bromo-dimethyl isoph...

Embodiment 2

[0045] The implementation of steps (1) to (8) in this example is the same as the implementation of steps (1) to (8) in Example 1.

[0046] (9) 2mg of 5,5',5"-(9H-carbazole-3,6,9-triyl)isophthalic acid obtained in step (8) and 2.916mg of Zn(NO 3 ) 2 2.5H 2 O was dissolved in 3mL N,N-dimethylacetamide (DMA), placed in a 5mL seed bottle, sealed and placed in an oven at 80°C for 72 hours. After taking it out, it was washed repeatedly with DMA to obtain a metal-organic framework material. .

[0047] The metal-organic framework material obtained in this example was solvent-exchanged with acetone, and the solvent was exchanged at least ten times every fifteen minutes, and then activated at 0°C for 24 hours under vacuum conditions, and then activated at room temperature for 12 hours, and finally After activation at 100°C for 2.5 hours, a metal-organic framework material with unsaturated metal sites and open pores was obtained. Using Micromeritics ASAP 2020 specific surface area an...

Embodiment 3

[0049] The implementation of steps (1) to (8) in this example is the same as the implementation of steps (1) to (8) in Example 1.

[0050] (9) 2 mg of 5,5', 5"-(9H-carbazole-3,6,9-triyl) isophthalic acid obtained in step (8) and 2.916 mg of NiCl 2 Dissolve in N,N-diethylacetamide (DEF) / acetonitrile (3mL, volume ratio: 9:1), place in a 5mL seed bottle, seal it and place it in an oven at 80°C for 72h, take it out Repeated washing with DEF yielded metal-organic framework materials.

[0051] The metal-organic framework material obtained in this example was solvent-exchanged with acetone, and the solvent was exchanged at least ten times every fifteen minutes, and then activated at 0°C for 24 hours under vacuum conditions, and then activated at room temperature for 12 hours, and finally After activation at 100°C for 2.5 hours, a metal-organic framework material with unsaturated metal sites and open pores was obtained. The Micromeritics ASAP 2020 specific surface area analyzer was ...

technical field

[0001] The invention relates to a microporous metal organic framework material and a preparation method thereof, in particular to a microporous metal organic framework material for methane and acetylene adsorption and storage and a preparation method thereof. Background technique

[0002] Methane is the main component of natural gas, and the C / H ratio of methane is very high. Compared with traditional energy sources such as petroleum, coal and other fossil fuels, methane is a clean fuel and environmentally friendly. At present, there are three main ways to store methane: liquefied methane, compressed methane and adsorbed methane. The liquefaction and compression method consumes a lot of energy and is complicated to operate, which has great potential safety hazards. The above problems prevent the liquefaction and compression of methane from being widely used. For commercial applications, traditional methane-absorbing materials include activated carbon and zeol...

Examples

Embodiment 1

[0030] (1) Dissolve 10g (50mmol) of 5-amino-isophthalic acid dimethyl ester into 225mL of hydrobromic acid solution with a mass concentration of 15%, stir and cool to 0°C, add dropwise 23mL of The aqueous solution of sodium nitrite of L carries out diazotization reaction, obtains diazonium salt solution;

[0031] (2) 9.8g cuprous bromide is dissolved in 90mL mass concentration and is in the hydrobromic acid solution of 15%, after being cooled to 0 ℃, in this solution, add dropwise the diazonium salt solution that step (1) obtains while stirring, React at 0°C for 30 minutes, and then react at room temperature for 12 hours. After the reaction, filter the organic layer and wash it repeatedly with water. Dissolve the organic layer in dichloromethane and wash with anhydrous MgSO 4 After drying and filtering, use petroleum ether and ethyl acetate (volume ratio 8:1) as the eluent to carry out column chromatography separation and purification to obtain 10.5 g of 5-bromo-dimethyl isoph...

Embodiment 2

[0045] The implementation of steps (1) to (8) in this example is the same as the implementation of steps (1) to (8) in Example 1.

[0046] (9) 2mg of 5,5',5"-(9H-carbazole-3,6,9-triyl)isophthalic acid obtained in step (8) and 2.916mg of Zn(NO 3 ) 2 2.5H 2 O was dissolved in 3mL N,N-dimethylacetamide (DMA), placed in a 5mL seed bottle, sealed and placed in an oven at 80°C for 72 hours. After taking it out, it was washed repeatedly with DMA to obtain a metal-organic framework material. .

[0047] The metal-organic framework material obtained in this example was solvent-exchanged with acetone, and the solvent was exchanged at least ten times every fifteen minutes, and then activated at 0°C for 24 hours under vacuum conditions, and then activated at room temperature for 12 hours, and finally After activation at 100°C for 2.5 hours, a metal-organic framework material with unsaturated metal sites and open pores was obtained. Using Micromeritics ASAP 2020 specific surface area an...

Embodiment 3

[0049] The implementation of steps (1) to (8) in this example is the same as the implementation of steps (1) to (8) in Example 1.

[0050] (9) 2 mg of 5,5', 5"-(9H-carbazole-3,6,9-triyl) isophthalic acid obtained in step (8) and 2.916 mg of NiCl 2 Dissolve in N,N-diethylacetamide (DEF) / acetonitrile (3mL, volume ratio: 9:1), place in a 5mL seed bottle, seal it and place it in an oven at 80°C for 72h, take it out Repeated washing with DEF yielded metal-organic framework materials.

[0051] The metal-organic framework material obtained in this example was solvent-exchanged with acetone, and the solvent was exchanged at least ten times every fifteen minutes, and then activated at 0°C for 24 hours under vacuum conditions, and then activated at room temperature for 12 hours, and finally After activation at 100°C for 2.5 hours, a metal-organic framework material with unsaturated metal sites and open pores was obtained. The Micromeritics ASAP 2020 specific surface area analyzer was ...

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