Preparation method of metal organic framework ZIF-8 (zero insert force-9) film

Abstract

The invention provides a novel preparation method of a high-performance continuous ZIF-8 (zero insert force-8) film for the high-performance separation and purification of gas, and mainly aims at solving the combination problem among a continuous even growth film, a film and a carrier of the ZIF-8 film. The preparation method is mainly characterized by comprising the following steps of: previously introducing growth point and a combination point on the surface of a porous carrier to form a thin layer of zinc oxide coating layer taken as a finished film, and growing in an inducing way to form the continuous even ZIF-8 film. An active point of the film homogeneous nucleation is introduced, the combination force problem between the film and the surface of the carrier is solved, and the surface of the carrier is modified by the coating layer, so that the high-quality film can be preferably formed. Compared with the conventional preparation method of the ZIF-8 film, the novel method adopted by the invention not only is high in film-forming effective mass, simple in process, and convenient for large-scale preparation and amplification, so that the method has a potential application prospect and a wide application value.

Description

technical field

[0001] The invention provides a method for preparing a metal-organic framework membrane material applied to high-performance gas separation. The main purpose is to solve the continuous formation of the membrane and the binding force between the membrane and the carrier. Background technique

[0002] Metal-organic framework (MOFs) materials have ultra-high specific surface area and huge pore volume, which can realize high-capacity storage of various gases. At the same time, its highly regular pore structure and the adjustable surface group can realize various Efficient separation of gas and liquid, and can greatly improve its material adsorption capacity and dynamic performance. Therefore, it is very attractive to apply MOFs materials to the field of gas storage and separation.

[0003] Application prospects.

[0004] ZIFs materials are a class of materials with relatively large specific surface area and pore volume in MOFs materials. Compared with other t...

Examples

Embodiment 1

[0038] (1) The porous support is α-Al with an average pore diameter of about 0.1 μm 2 o 3 Ceramic carrier tube. Before the synthesis, the carrier is firstly cleaned with deionized water under ultrasonic vibration, dried and roasted for use.

[0039] (2) Configuration and pulling of zinc-containing sol to introduce the surface of the carrier: a certain amount of zinc acetate is dissolved in ethylene glycol methyl ether solvent and ethanolamine is used as a stabilizer, and the mass fraction of zinc is 14.3%. , and then dipped and pulled to coat the pre-configured zinc sol, dried at 100°C for 2 hours, and then placed in a muffle furnace for 100 minutes at 400°C, and the heating rate was set at 0.5°C / min. Cool down to room temperature; repeat 2-3 times.

[0040] (3) Film formation on the surface of the porous ceramic tube carrier: Put the porous ceramic tube coated with zinc oxide layer into the prepared 0.5M 2-methylimidazole methanol solution for activation at 50°C for 1 hour...

Embodiment 2

[0043] (1) The porous support is α-Al with an average pore diameter of about 0.1 μm 2 o 3 Ceramic carrier tube. Before the synthesis, the carrier is firstly cleaned with deionized water under ultrasonic vibration, dried and roasted for use.

[0044](2) Configuration and introduction of zinc-containing synthetic solution to the surface of the carrier: use hexamethylenetetraammonium (C6H12N4) and zinc nitrate as raw materials, and prepare a zinc oxide layer growth solution according to the ratio of 2Zn(NO3)2:0.3C6H12N4:230H2O, Put the porous carrier in the zinc oxide layer growth solution and react at 90°C for 6 hours to grow a zinc oxide layer;

[0045] (3) Synthesis of ZIF-8 membrane: Put the porous ceramic carrier with the zinc oxide layer into the prepared 0.5M 2-methylimidazole methanol solution for activation at 50°C for 1 hour, take it out and dry it in the air; 0.65HCOONa: 1.0ZnCl2: 1.52-meIM: 450MeOH to configure a stable ZIF-8 membrane solution, and aged for 2h. Th...

Embodiment 3

[0048] (1) The porous support is α-Al with an average pore diameter of about 0.1 μm 2 o 3 Ceramic carrier tube. Before the synthesis, the carrier is firstly cleaned with deionized water under ultrasonic vibration, dried and roasted for use.

[0049] (2) Configuration and pulling of zinc-containing sol to introduce the surface of the carrier: a certain amount of zinc acetate is dissolved in ethylene glycol methyl ether solvent and ethanolamine is used as a stabilizer, and the mass fraction of zinc is 14.3%. , and then dipped and pulled to coat the pre-configured zinc sol, dried at 100°C for 2 hours, and then placed in a muffle furnace for 100 minutes at 400°C, and the heating rate was set at 0.5°C / min. Cool down to room temperature; repeat 2-3 times.

[0050] (3) Configuration of zinc-containing synthetic solution and introduction to the surface of the carrier: use hexamethylenetetraammonium (C6H12N4) and zinc nitrate as raw materials, and prepare a zinc oxide layer growth s...

technical field

[0001] The invention provides a method for preparing a metal-organic framework membrane material applied to high-performance gas separation. The main purpose is to solve the continuous formation of the membrane and the binding force between the membrane and the carrier. Background technique

[0002] Metal-organic framework (MOFs) materials have ultra-high specific surface area and huge pore volume, which can realize high-capacity storage of various gases. At the same time, its highly regular pore structure and the adjustable surface group can realize various Efficient separation of gas and liquid, and can greatly improve its material adsorption capacity and dynamic performance. Therefore, it is very attractive to apply MOFs materials to the field of gas storage and separation.

[0003] Application prospects.

[0004] ZIFs materials are a class of materials with relatively large specific surface area and pore volume in MOFs materials. Compared with other t...

Examples

Embodiment 1

[0038] (1) The porous support is α-Al with an average pore diameter of about 0.1 μm 2 o 3 Ceramic carrier tube. Before the synthesis, the carrier is firstly cleaned with deionized water under ultrasonic vibration, dried and roasted for use.

[0039] (2) Configuration and pulling of zinc-containing sol to introduce the surface of the carrier: a certain amount of zinc acetate is dissolved in ethylene glycol methyl ether solvent and ethanolamine is used as a stabilizer, and the mass fraction of zinc is 14.3%. , and then dipped and pulled to coat the pre-configured zinc sol, dried at 100°C for 2 hours, and then placed in a muffle furnace for 100 minutes at 400°C, and the heating rate was set at 0.5°C / min. Cool down to room temperature; repeat 2-3 times.

[0040] (3) Film formation on the surface of the porous ceramic tube carrier: Put the porous ceramic tube coated with zinc oxide layer into the prepared 0.5M 2-methylimidazole methanol solution for activation at 50°C for 1 hour...

Embodiment 2

[0043] (1) The porous support is α-Al with an average pore diameter of about 0.1 μm 2 o 3 Ceramic carrier tube. Before the synthesis, the carrier is firstly cleaned with deionized water under ultrasonic vibration, dried and roasted for use.

[0044](2) Configuration and introduction of zinc-containing synthetic solution to the surface of the carrier: use hexamethylenetetraammonium (C6H12N4) and zinc nitrate as raw materials, and prepare a zinc oxide layer growth solution according to the ratio of 2Zn(NO3)2:0.3C6H12N4:230H2O, Put the porous carrier in the zinc oxide layer growth solution and react at 90°C for 6 hours to grow a zinc oxide layer;

[0045] (3) Synthesis of ZIF-8 membrane: Put the porous ceramic carrier with the zinc oxide layer into the prepared 0.5M 2-methylimidazole methanol solution for activation at 50°C for 1 hour, take it out and dry it in the air; 0.65HCOONa: 1.0ZnCl2: 1.52-meIM: 450MeOH to configure a stable ZIF-8 membrane solution, and aged for 2h. Th...

Embodiment 3

[0048] (1) The porous support is α-Al with an average pore diameter of about 0.1 μm 2 o 3 Ceramic carrier tube. Before the synthesis, the carrier is firstly cleaned with deionized water under ultrasonic vibration, dried and roasted for use.

[0049] (2) Configuration and pulling of zinc-containing sol to introduce the surface of the carrier: a certain amount of zinc acetate is dissolved in ethylene glycol methyl ether solvent and ethanolamine is used as a stabilizer, and the mass fraction of zinc is 14.3%. , and then dipped and pulled to coat the pre-configured zinc sol, dried at 100°C for 2 hours, and then placed in a muffle furnace for 100 minutes at 400°C, and the heating rate was set at 0.5°C / min. Cool down to room temperature; repeat 2-3 times.

[0050] (3) Configuration of zinc-containing synthetic solution and introduction to the surface of the carrier: use hexamethylenetetraammonium (C6H12N4) and zinc nitrate as raw materials, and prepare a zinc oxide layer growth s...

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