WO2016041317A1

WO2016041317A1 - Preparation and modification methods for metal-organic framework material bi-btc adsorbing co2

Info

Publication number: WO2016041317A1
Application number: PCT/CN2015/072270
Authority: WO
Inventors: 尹双凤; 杨泛明; 刘�英; 陈浪
Original assignee: 湖南大学
Priority date: 2014-09-19
Filing date: 2015-02-05
Publication date: 2016-03-24
Also published as: CN104226260A; CN104226260B

Abstract

Provided is a preparation method for a metal-organic framework material Bi-BTC adsorbing CO₂. The preparation method comprises the following steps: dissolving Bi(NO₃)₃•5H₂O in a mixed solution of anhydrous ethanol and ethylene glycol or a mixed solution of ethylene glycol and glycerol, to form a solution A; dissolving 1,3,5-benzenetricarboxylic acid in anhydrous ethanol or N,N-dimethylformamide to form a solution B; slowly adding the solution B into the solution A at room temperature to obtain a first mixed solution; crystalizing the first mixed solution at 120°C-130°C for 2-3 days to obtain a first solid product; washing the first product with an alcoholic solution, and placing the washed first solid product in a drying oven at 110°C-130°C and keeping for 10 h-16 h to obtain the metal-organic framework material Bi-BTC. The material has a better adsorption capacity for CO₂ at a relatively low temperature and in a relatively low CO₂pressure environment.

Description

Preparation and modification method of metal-organic framework material Bi-BTC adsorbing CO ₂

Technical field

[0001] The present invention relates to a CO ₂ adsorbent material, and more particularly to a method for preparing a metal-organic framework material Bi-BTC capable of efficiently adsorbing CO ₂ in a lower temperature and a lower pressure environment, and a modified product thereof.

Background technique

[0002] Carbon dioxide (CO ₂ ) is currently the most important greenhouse gas in the world, and it is also the cheapest and most abundant resource in the C1 family. Therefore, it is used in various fields, such as CO ₂ as a fire extinguishing agent and food preservation. Agents, oil field injections and important industrial production materials. Therefore, CO ₂ separation and capture has become the focus of attention of all countries, and the development of efficient CO ₂ separation and capture technology is the key.

[0003] CO ₂ separation and capture is mainly carried out by two methods of CO ₂ absorption or CO ₂ adsorption. At present, the industry mainly uses liquid ammonia to absorb CO ₂ , but liquid ammonia is more serious to equipment corrosion, and more by-products are generated in the CO ₂ absorption process, and a large amount of water vapor is consumed in the regeneration process to waste resources. CO ₂ adsorption is a physical or chemical process that utilizes a solid adsorbent to interact with CO ₂ molecules on the surface of the adsorbent. Different types of adsorbents have different CO ₂ adsorption properties, and the design of CO ₂ adsorption materials with large adsorption capacity, low adsorption-desorption temperature and low energy consumption is being explored in the industry.

[0004] Metal-organic framework (MOFs) materials are a new class of porous functional materials constructed from metal ion units and organic ligands. These materials have a large specific surface area, a regular internal arrangement, and a special topology. When gas molecules reach the surface of MOFs, they can interact with the active sites on their surface, making MOFs materials perform better in gas separation.

[0005] The properties of MOFs are related to the pore size and morphology of the material, the bare metal sites on the surface, the nature of the organic ligand, and the type of solvent. The pore size, morphology and structure of MOFs can be effectively changed by adjusting the metal ion species, organic ligand species or materials. Therefore, various MOFs materials can be produced through reasonable control of the above influencing factors and applied to various application fields. For example, DMF can be used as a solvent, and Zn(NO ₃ ) ₂ and terephthalic acid (H ₂ BDC) can be used as raw materials to synthesize CO _{2 .}

MOF-5 with better adsorption performance; DMF as solvent, pyridine as deprotonating reagent, Zn(N0 ₃ ) ₂ And adenine as a raw material can be synthesized for CO ₂ and 11 ₂

Zn-Adeninate macrocyclic MOFs with good adsorption properties. Therefore, the specific properties of the MOFs can be changed by changing the material structure.

Problem solution

Technical solution

[0006] An object of the present invention is to provide a method for preparing a metal-organic framework material Bi-BTC having high-efficiency CO ₂ adsorption performance and a modification thereof.

[0007] In order to achieve the above object, the present invention provides a method for preparing a metal-organic framework material Bi-BTC adsorbing CO ₂ , comprising the following steps:

[0008] Bi(NO ₃ ) ₃ ·5Η _{20 is} dissolved in the first solvent to form a solution hydrazine;

[0009] 1,3,5-benzenetricarboxylic acid (H ₃ BTC) is dissolved in a second solvent to form a solution B;

[0010] At room temperature, the solution B is slowly added to the solution A to obtain a mixed solution, and the mixed solution is crystallized at 120 ° C to 130 ° C for 2 to 3 days to obtain a first solid product, which is treated with an alcohol solution. The first solid product is washed, and the washed first solid product is placed in a drying oven at 110 ° C to 130 ° C to maintain 101! ~ 1

6h, the metal-organic framework material Bi-BTC was obtained.

[0011] In the above preparation method, the first solvent is a mixed solution of absolute ethanol and ethylene glycol or a mixed solution of anhydrous ethylene glycol and glycerin.

[0012] In the above preparation method, the volume ratio of the absolute ethanol to ethylene glycol is 5: [3~2], or the volume ratio of the absolute ethanol to glycerol is 5: [3~2] .

[0013] In the above preparation method, the second solvent is absolute ethanol or hydrazine, hydrazine-dimethylformamide (DMF).

[0014] In the above preparation method, the alcohol solution is anhydrous methanol, absolute ethanol or anhydrous isopropanol.

[0015] In the above preparation method, the first solid product after washing the alcohol solution is placed in a drying oven at 120 ° C.

, held for 12h, to get the metal-organic framework material Bi-BTC.

[0016] The present invention also provides a metal-organic framework material Bi-BTC which adsorbs CO ₂ , which is obtained by any of the preparation methods described above.

[0017] The present invention further provides a method for modifying the CO ₂ -adsorbing metal-organic framework material Bi-BTC prepared above to obtain Am/Bi-BTC, comprising the following steps:

[0018] The organic amine is dissolved in a third solvent to form a solution C; [0019] The prepared Bi-BTC is added to the solution C to obtain a turbid liquid D;

[0020] The turbid liquid D is refluxed at 80 ° C to 100 ° C 81! ~ 10h, the second solid product is obtained, the solvent is removed by rotary evaporation, and the obtained solid is placed in a drying oven at 80 ° C ~ 100 ° C, maintaining 81! ~10h, a metal-organic frame modified material Am/Bi-BTC was obtained.

[0021] In the above modification method, the organic amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethyleneimine.

[0022] In the above modification method, the third solvent is deionized water, methanol or absolute ethanol.

[0023] In the above modification method, the mass ratio of the organic amine of the reaction amount to the mass ratio of Bi-BTC is between 1:6 and 1:1.

[0024] In the above modification method, after the second solid product is subjected to rotary evaporation to remove the solvent, the obtained solid is placed in a drying oven at 80 ° C for 12 hours to obtain a modified material of Am/Bi-BTC.

Advantageous effects of the invention

Beneficial effect

[0025] According to the experimental results, the metal-organic framework material provided by the present invention has C0 ₂ in a lower temperature and low pressure environment.

The adsorption capacity is large, the adsorption-desorption temperature is low, and the like, the method solves the common shortage of low pressure adsorption of CO ₂ and high desorption temperature, and has good industrial application prospects.

Brief description of the drawing

DRAWINGS

1 is a graph showing the adsorption breakthrough of Bi-BTC to CO ₂ in Example 1 of the present invention.

Embodiments of the invention

[0027] - Organic frame leak 1 preparation:

Preparation Example 1

[0029] a 0.81g Bi (NO ₃ ) ₃ dissolved in 50ml of absolute ethanol and 20ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0030] b 1.05g H ₃ BTC dissolved in 30ml of absolute ethanol, stirred and dissolved, forming a solution B; [0031] c at room temperature, B solution is added dropwise to the A solution, stirred, so that the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0032] d at 120 ° C, a mixed solution of solution A and solution B is crystallized for 2 days to obtain a solid product;

[0033] e. The solid product obtained in step d was washed with anhydrous methanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 2

[0035] a 2.43g Bi (NO ₃ ) ₃ dissolved in 50ml of absolute ethanol and 20ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0036] b 1.05g H ₃ BTC dissolved in 30ml of absolute ethanol, stirred and dissolved, forming a solution B;

[0037] c at room temperature, B solution is added dropwise to the A solution, stirred, so that the A solution and the B solution are evenly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0038] d at 120 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product;

[0039] e. The solid product obtained in step d was washed with anhydrous methanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 3

[0041] a 1.62g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 30ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0042] b 1.05g H ₃ BTC dissolved in 30ml of absolute ethanol, stirred and dissolved, forming a solution B;

[0043] c at room temperature, B solution is added dropwise to the A solution, stirred, so that the A solution and the B solution are evenly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0044] d at 130 ° C, a mixed solution of solution A and solution B is crystallized for 2 days to obtain a solid product;

[0045] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 4

[0047] a 2.43g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 20ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0048] b 1.05g H3BTC dissolved in 30ml of absolute ethanol, stirred and dissolved, forming a solution B;

[0049] c at room temperature, B solution is added dropwise to the A solution, stirred, so that the A solution and the B solution are uniformly mixed , obtaining a mixed solution of the A solution and the B solution;

[0050] d at 130 ° C, a mixed solution of solution A and solution B crystallized for 3 days, to obtain a solid product;

[0051] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 5

[0053] a 0.81g Bi (N03) 3 dissolved in 50ml of ethanol and 20ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0054] b 1.05g H3BTC dissolved in 30ml DMF, stirred and dissolved, forming a solution B;

[0055] c at room temperature, the B solution is added dropwise to the A solution, stirred, and the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0056] d at 120 ° C, a mixed solution of solution A and solution B is crystallized for 2 days to obtain a solid product;

[0057] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a 120 ° C dry box for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 6

[0059] a 2.43g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 20ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0060] b 1.05g H ₃ BTC dissolved in 30ml DMF, stirred and dissolved, forming a solution B;

[0061] c at room temperature, B solution is added dropwise to the A solution, stirred, so that the A solution and the B solution are evenly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0062] d at 120 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product;

[0063] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 7

[0065] a 2.43g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 30ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0066] b 1.05g H ₃ BTC dissolved in 30ml DMF, stirred and dissolved, forming a solution B;

[0067] c at room temperature, the B solution is added dropwise to the A solution, stirred, the A solution and the B solution are uniformly mixed to obtain a mixed solution of the A solution and the B solution; [0068] d at 130 ° C, a mixed solution of solution A and solution B is crystallized for 2 days to obtain a solid product;

[0069] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 8

[0071] a 1.62g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 20ml of ethylene glycol in a mixed solution, stirred and dissolved, forming a solution A;

[0072] b 1.05g H ₃ BTC dissolved in 30ml DMF, stirred and dissolved, forming a solution B;

[0073] c at room temperature, the B solution is added dropwise to the A solution, stirred, and the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0074] d at 130 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product;

[0075] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 9

[0077] a 2.43g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 20ml of glycerol in a mixed solution, stirred and dissolved, forming a solution A;

[0078] b 1.05g H ₃ BTC dissolved in 30ml of absolute ethanol, stirred and dissolved, forming a solution B;

[0079] c at room temperature, the B solution is added dropwise to the A solution, stirred, and the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0080] d at 120 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product;

[0081] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 10

[0083] a 0.81g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 20ml of glycerol in a mixed solution, stirred and dissolved, forming a solution A;

[0084] b 1.05g H ₃ BTC dissolved in 30ml of absolute ethanol, stirred and dissolved, forming a solution B;

[0085] c at room temperature, the B solution is added dropwise to the A solution, stirred, and the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0086] d at 130 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product; [0087] e. The solid product obtained in step d was washed with absolute ethanol, and then the solid product washed with absolute ethanol was placed in a drying oven at 120 ° C for 12 h to obtain a metal-organic framework material Bi- BTC.

Preparation Example 11

[0089] a 2.43g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 20ml of glycerol in a mixed solution, stirred and dissolved, forming a solution A;

[0090] b 1.05g H ₃ BTC dissolved in 30ml DMF, stirred and dissolved, forming a solution B;

[0091] c at room temperature, the B solution is added dropwise to the A solution, stirred, and the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0092] d at 120 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product;

[0093] e. The solid product obtained in step d is washed with anhydrous isopropanol, and then the solid product washed with anhydrous ethanol is placed in a 120 ° C dry box for 12 h to obtain a metal-organic framework material. Bi-BTC.

Preparation Example 12.

[0095] a 1.62g Bi (NO ₃ ) ₃ dissolved in 50ml of ethanol and 30ml of glycerol in a mixed solution, stirred and dissolved, forming a solution A;

[0096] b 1.05g H ₃ BTC dissolved in 30ml DMF, stirred and dissolved, forming a solution B;

[0097] c at room temperature, the B solution is added dropwise to the A solution, stirred, and the A solution and the B solution are uniformly mixed

, obtaining a mixed solution of the A solution and the B solution;

[0098] d at 130 ° C, a mixed solution of solution A and solution B is crystallized for 3 days to obtain a solid product;

[0099] e. The solid product obtained in step d was washed with anhydrous isopropanol, and then the solid product washed with absolute ethanol was placed in a 120 ° C dry box for 12 h to obtain a metal-organic framework material. Bi-BTC.

[0100] Gold) S-Organic Framework Modification Material Preparation of Am/Bi-BTC:

Preparation Example 13

[0102] a. Ethylenediamine is dissolved in 10 g of deionized water at room temperature to obtain an alcohol solution of ethylenediamine. The above operation was repeated to prepare 6 parts of an alcohol solution of ethylenediamine. To each of the prepared ethylenediamine alcohol solutions, 0.3 g of the metal-organic framework material Bi-BTC prepared in Preparation Example 1 was added, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of ethylenediamine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0103] b 6 parts of the solid product obtained in step a is subjected to rotary evaporation, the solvent is removed, and the solid product after removing the solvent is separately placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC Preparation Example 14

[0105] a. Ethylenediamine is dissolved in 10 g of absolute ethanol at room temperature to obtain an alcohol solution of ethylenediamine. The above operation was repeated to prepare 6 parts of an alcohol solution of ethylenediamine. To each of the prepared ethylene glycol diamine alcohol solutions, 0.3 g of the metal-organic framework material Bi-BTC prepared in Preparation Example 2 was placed, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of ethylenediamine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0106] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 15

a. Dissolving diethylenetriamine in 10 g of deionized water at room temperature to obtain an alcohol solution of diethylenetriamine. The above operation was repeated to prepare 6 parts of an alcohol solution of diethylenetriamine. To each of the prepared diethylenetriamine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 3 was placed, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of diethylenetriamine and Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0109] b 6 parts of the solid product obtained in step a is subjected to rotary evaporation, the solvent is removed, and the solid product after removing the solvent is separately placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 16

a. Dissolving diethylenetriamine in 10 g of absolute ethanol at room temperature to obtain an alcohol solution of diethylenetriamine. The above operation was repeated to prepare 6 parts of an alcohol solution of diethylenetriamine. To each of the prepared diethylenetriamine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 4 was placed, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of diethylenetriamine and Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0112] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 17 a. Dissolving diethylenetriamine in 10 g of methanol at room temperature to obtain an alcohol solution of diethylenetriamine. The above operation was repeated to prepare 6 parts of an alcohol solution of diethylenetriamine. To each of the prepared diethylenetriamine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 5 was placed, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of diethylenetriamine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0115] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 18

a. Dissolving triethylenetetramine in 10 g of absolute ethanol at room temperature to obtain an alcohol solution of triethylenetetramine. The above operation was repeated to prepare 6 parts of an alcohol solution of triethylenetetramine. To each of the prepared triethylenetetramine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 6 was placed, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of triethylenetetramine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0118] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 19

a. Dissolving triethylenetetramine in 10 g of absolute ethanol at room temperature to obtain an alcohol solution of triethylenetetramine. The above operation was repeated to prepare 6 parts of an alcohol solution of triethylenetetramine. To each of the prepared triethylenetetramine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 7 was placed, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of triethylenetetramine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0121] b 6 parts of the solid product obtained in step a is subjected to rotary evaporation, the solvent is removed, and the solid product after removing the solvent is separately placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 20

a. Dissolving triethylenetetramine in 10 g of absolute ethanol at room temperature to obtain an alcohol solution of triethylenetetramine. Repeat In the above operation, 6 parts of an alcohol solution of triethylenetetramine was prepared. To each of the prepared triethylenetetramine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 8 was added, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of triethylenetetramine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0124] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 h to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 21

a. Dissolving tetraethylenepentamine in 10 g of methanol at room temperature to obtain an alcohol solution of tetraethylenepentamine. The above operation was repeated to prepare 6 parts of an alcohol solution of tetraethylenepentamine. To each of the prepared tetraethylenepentamine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 9 was added, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of tetraethylenepentamine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0127] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 h to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 22

a. Dissolving tetraethylenepentamine in 10 g of methanol at room temperature to obtain an alcohol solution of tetraethylenepentamine. The above operation was repeated to prepare 6 parts of an alcohol solution of tetraethylenepentamine. To each of the prepared tetraethylenepentamine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 10 was added, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of tetraethylenepentamine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0130] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 h to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 23

[0132] a. Polyethyleneimine was dissolved in 10 g of methanol at room temperature to obtain an alcohol solution of polyethyleneimine. The above operation was repeated to prepare 6 parts of an alcohol solution of polyethyleneimine. Add in each alcohol solution of polyethyleneimine prepared 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 11 was refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of polyethyleneimine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0133] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 hours to obtain a metal-organic frame. Material Am/Bi-BTC

Preparation Example 24

[0135] a. Polyethyleneimine was dissolved in 10 g of methanol at room temperature to obtain an alcohol solution of polyethyleneimine. The above operation was repeated to prepare 6 parts of an alcohol solution of polyethyleneimine. To each of the prepared polyethyleneimine alcohol solutions, 0.3 g of the metal mechanical frame material Bi-BTC prepared in Preparation Example 12 was added, and refluxed at 80 ° C for 8 hours to obtain 6 parts of a solid product. The mass ratio of polyethyleneimine to Bi-BTC added is 1:6, 1:5, 1:4, 1:3, 1:2 or 1:1, respectively.

[0136] b 6 parts of the solid product obtained in step a was subjected to rotary evaporation, the solvent was removed, and the solid product after removing the solvent was placed in a drying oven at 80 ° C for 10 h to obtain a metal-organic frame. Material Am/Bi-BTC

[0137] CO-TPD determination of metal-organic framework materials

Example 1

[0139] An appropriate amount of the metal-organic framework material Bi-BTC prepared by Preparation Example 1 was placed in a U-tube of A _U toCh _e mH2920, and a high-purity Ar purged metal-organic framework material Bi-BTC surface was obtained. The same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0140] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

, keep 10min, C0 ₂ volume percentage in 5% C0 ₂ -He gas is 5%, He volume percentage is 95

0/

/0;

[0141] The high-purity Ar was introduced, and the temperature was raised to 100 ° C for 60 min, and the CO ₂ adsorption breakthrough curve of the obtained Bi-BTC was as shown in FIG. 1 .

Example 2

[0143] An appropriate amount of the metal mechanical frame material Bi-BTC prepared by Preparation Example 2 was placed in a U-tube of A _U toCh _e mII2920, and a high-purity Ar purged metal-organic framework material Bi-BTC surface was obtained. Warm up to 100 °C After 60 minutes, the temperature is lowered to 50 ° C;

[0144] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0145] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 3

[0147] An appropriate amount of the metal-organic framework material Bi-BTC prepared by Preparation Example 3 was placed in a U-tube of A _U toCh _e mH2920, and a high-purity Ar purged metal-organic framework material Bi-BTC surface was obtained. The same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0148] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0149] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 4

[0151] An appropriate amount of the metal mechanical frame material Bi-BTC prepared by Preparation Example 4 was placed in a U-tube of A _U toCh _e mII2920, and a high-purity Ar purged metal-organic framework material Bi-BTC surface was obtained. The same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0152] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0153] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 5

[0155] An appropriate amount of the metal-organic framework modified material Bi-BTC prepared by Preparation Example 5 was placed in a U-shaped tube of AutoCh emII2920, and a high-purity Ar-purged metal-organic framework modified material Bi-BTC was introduced. Surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C; [0156] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0157] High purity Ar was passed in, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 6

[0159] An appropriate amount of the metal-organic framework modified material Bi-BTC prepared by Preparation Example 6 was placed in a U-shaped tube of AutoCh emII2920, and a high-purity Ar-purged metal-organic framework modified material Bi-BTC was introduced. Surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0160] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0161] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 7

[0163] An appropriate amount of the metal-organic framework modified material Bi-BTC prepared by Preparation Example 7 was separately placed in a U-shaped tube of AutoCh emII2920, and a high-purity Ar-purged metal-organic framework modified material Bi-BTC was introduced. Surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0164] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0165] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 8

[0167] An appropriate amount of the metal-organic framework modified material Bi-BTC prepared by Preparation Example 8 was placed in a U-shaped tube of AutoCh emII2920, and a high-purity Ar-purged metal-organic framework modified material Bi-BTC was introduced. Surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0168] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1 , keep 10min, C0 ₂ volume percentage in 5% C0 ₂ -He gas is 5%, He volume percentage is 95

0/

/0;

[0169] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 9

[0171] An appropriate amount of the metal-organic framework modified material Bi-BTC prepared by Preparation Example 9 was placed in a U-shaped tube of AutoCh em II2920, and a high-purity Ar-purged metal-organic frame modified material Bi-BTC was introduced. Surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0172] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0173] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 10

[0175] An appropriate amount of the metal mechanical frame modifying material Bi-BTC prepared by the preparation example 10 was placed in a U-shaped tube of AutoC h _e mII2920, and a high-purity Ar-purged metal-organic frame modified material Bi was introduced. -BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0176] 5% CO ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0177] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 11

[0179] An appropriate amount of the metal mechanical frame modification material Bi-BTC prepared by Preparation Example 11 was respectively placed in a U-shaped tube of AutoC h _e mII2920, and a high-purity Ar-purged metal-organic frame modified material Bi was introduced. -BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0180] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

, keep 10min, C0 ₂ volume percentage in 5% C0 ₂ -He gas is 5%, He volume percentage is 95 0/

7o;

[0181] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 12

[0183] An appropriate amount of the metal mechanical frame modification material Bi-BTC prepared by Preparation Example 12 was placed in a U-shaped tube of AutoC h _e mII2920, and a high-purity Ar-purged metal-organic frame modified material Bi was introduced. -BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0184] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0185] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min. The CO ₂ adsorption breakthrough curve of the obtained Bi-BTC is similar to the curve shown in FIG.

Example 13

[0187] An appropriate amount of the metal mechanical frame modifying material Am/Bi-BTC prepared by Preparation Example 13 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0188] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0189] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation Example 1. , between 2.5-4m mol g - ¹ .

Example 14

[0192] An appropriate amount of the metal mechanical frame modifying material Am/Bi-BTC prepared by Preparation Example 14 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0193] 5% CO ₂ -He gas, gas pressure 0.2 MPa, gas flow rate 50 ml * min - ¹ , keep 10min, C0 ₂ volume percentage in 5% C0 ₂ -He gas is 5%, He volume percentage is 95

0/

/0;

[0194] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation 2. , between 2.5-4m mol g - ¹ .

Example 15

[0197] An appropriate amount of the metal mechanical frame modifying material Am/Bi-BTC prepared by Preparation Example 15 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0198] 5% CO ₂ -He gas, gas pressure 0.2 MPa, gas flow rate 50 ml * min - ¹

0/

/0;

[0199] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0200] The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation 3. , between 2.5-4m mol g - ¹ .

Example 16

[0202] An appropriate amount of the metal mechanical frame modification material Am/Bi-BTC prepared by Preparation Example 16 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0203] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ¹

0/

/0;

[0204] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

The CO ₂ adsorption of the metal-organic framework modification material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanism frame material Bi-BTC in Preparation Example 4. , between 2.5-4m mol g - ¹ . Example 17

[0207] An appropriate amount of the metal mechanical frame modifying material Am/Bi-BTC prepared by Preparation Example 17 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0208] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0209] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0210] The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation Example 5. , between 2.5-4m mol g - ¹ .

Example 18

[0212] An appropriate amount of the metal mechanical frame modifying material Am/Bi-BTC prepared by Preparation Example 18 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0213] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0214] The high purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0215] The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation Example 6. , between 2.5-4m mol g - ¹ .

Example 19

[0217] An appropriate amount of the metal mechanical frame modifying material Am/Bi-BTC prepared by Preparation Example 19 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0218] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

7o;

[0219] The high purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0220] The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation Example 7. , between 2.5-4m mol g - ¹ .

Example 20

An appropriate amount of the metal-organic framework modified material Am/Bi-BTC prepared by Preparation Example 20 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic framework modified material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0223] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ¹

0/

/0;

[0224] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0225] The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation Example 8. , between 2.5-4m mol g - ¹ .

Example 21

An appropriate amount of the metal-organic framework modified material Am/Bi-BTC prepared by Preparation Example 21 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic framework modified material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0228] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0229] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0230] The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal mechanical framework material Bi-BTC in Preparation Example 9. , between 2.5-4m mol g - ¹ .

Example 22 An appropriate amount of the metal-organic framework modifying material Am/Bi-BTC prepared by Preparation Example 22 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0233] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0234] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal-organic framework material Bi-BTC in Preparation Example 10. , between 2.5-4 mmol g - ¹ .

Example 23

An appropriate amount of the metal-organic framework modifying material Am/Bi-BTC prepared by Preparation Example 23 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0238] 5% C0 ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ^-1

0/

/0;

[0239] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

The CO ₂ adsorption of the metal-organic framework modifying material Am/Bi-BTC can be saturated within 10 min, and the adsorption amount is significantly increased compared with the adsorption amount of the metal-organic framework material Bi-BTC in Preparation 11. , between 2.5-4 mmol g - ¹ .

Example 24

An appropriate amount of the metal-organic framework modifying material Am/Bi-BTC prepared by Preparation Example 24 was placed in a U-shaped tube of AutoChem II2920, and a high-purity Ar-purged metal-organic frame modifying material Am was introduced. /Bi-BTC surface, the same temperature is raised to 100 ° C, after 60 min, the temperature is lowered to 50 ° C;

[0243] 5% CO ₂ -He gas was introduced, the gas pressure was 0.2 MPa, and the gas flow rate was 50 ml*min ¹

, keep 10min, C0 ₂ volume percentage in 5% C0 ₂ -He gas is 5%, He volume percentage is 95 [0244] High purity Ar was passed, and the temperature was raised to 100 ° C for 60 min.

[0245] Metal-Organic Framework Modification Material Am/Bi-BTC. 0 ₂ adsorption can reach saturation within 10 min, and the adsorption amount is significantly increased compared with the amount of metal-organic framework material Bi-BTC adsorbed in Preparation 12, which is between 2.5-4 mmol g ^-1 .

In order to further illustrate the superiority of the metal-organic framework material of the present invention, the following adsorbents were selected as comparative examples.

Comparative Example 1

1.16 g of 4,4'-dihydroxybiphenyl, 2.00 g of potassium hydrogencarbonate, 4 g of dry ice and 1,2,4-trichlorobenzene were added to a 23 ml polytetrafluoroethylene liner, and the temperature was raised to 255 ° C, kept for 17h. The mixture was cooled to room temperature, vacuum filtered and washed with diethyl ether. Further, the obtained solid was placed in 300 ml of distilled water, dilute hydrochloric acid was added thereto to have a pH of about 1 to 2, and filtered to obtain a crude product. The obtained crude product was recrystallized from 50 ml of acetone and 50 ml of water to give the white solid product 4,4'-dihydroxy-(1, dec-diphenyl)-3,3'-dicarboxylic acid (H4dobpdc;).

Taking 24 mg of the obtained H ₄ dobpdc, 60 mg of MgBr ₂ ·6Η ₂₀ and 3 ml of cerium, a mixture of cerium-diethylformamide and ethanol (ratio 1:1) in a 10 ml polytetrafluoroethylene In the vessel, the reaction vessel is sealed, and the reactant is reacted at 120 ° C for 30 min under microwave irradiation, and the temperature is lowered to room temperature. The obtained crystal is washed with hot hydrazine, hydrazine-diethylformamide, and dried to obtain a metal-organic framework. Material Mg ^dobpdcXDEF ^EF ^H ^ . The obtained material was dried at 420 ° C for 65 min to obtain Mg ₂ (dobpd _C ), which was used.

[0250] From the Mg ₂ (dobpdc) material C0 ₂ adsorption experiment results, the temperature is 313.15K, CO ₂

The pressure was 0.15 atm 吋 and the adsorption amount was 3.14 mmol g - '.

Comparative Example 2

2.10 mmol of Al(NO ₃ ) ₃ dissolved in 15 ml of DMF, 3.12 mmol

2-Aminoterephthalic acid was dissolved in 15 ml of DMF. The two solutions were mixed, and the mixture was crystallized at 130 ° C for 3 days to give a yellow solid product. After washing the resulting product with acetone, the acetone was removed under a reduced pressure environment. The solid after removing acetone was dissolved in methanol, and after refluxing overnight, the obtained solid was dried at 110 ° C for 8 hours to obtain a material MIL-53, which was used.

[0253] From the C0 ₂ adsorption isotherm of MIL-53, when the CO ₂ pressure is 1 bar (about 1 latm), the CO ₂ adsorption amount is less than 2.3 mmol*g -

Claims

Claim

[Claim 1] A method for preparing a metal-organic framework material Bi-BTC which adsorbs CO ₂ , comprising the following steps:

Dissolving Bi(NO ₃ ) 3-5H ₂ 0 in the first solvent to form solution A;

Dissolving 1,3,5-benzenetricarboxylic acid in a second solvent to form a solution B;

The solution B is slowly added to the solution A at room temperature to obtain a mixed solution; the mixed solution is crystallized at 120 ° C to 130 ° C for 2 to 3 days to obtain a first solid product; the first solid product is used for alcohol After washing the solution, place it in a drying oven at 110 ° C ~ 130 ° C, keep 101! ~ 16h, get the metal-organic framework material Bi-BTC.

[Claim 2] The adsorption of CO according to claim 1 Metal ₂ - Preparation of an organic framework material of Bi-BTC, wherein said first solvent is a mixture of anhydrous ethanol and ethylene glycol, or a mixed solution of absolute ethanol and glycerin; the volume ratio of the anhydrous ethanol to ethylene glycol is 5: [3~2], or the volume ratio of the anhydrous ethanol to glycerol is 5: [3 ~2

The method of preparing an organic framework material of Bi-BTC, wherein the second solvent is ethanol or Ν, Ν- dimethylformamide - metal adsorbed CO ₂ according to the claim 1 [claim 3] Amide.

[Claim 4] The CO adsorption according to claim 1 Metal ₂ - Preparation of an organic framework material of Bi-BTC, wherein said alcohol solution is anhydrous methanol, anhydrous ethanol or anhydrous isopropanol .

[Claim 5] according to claim 1, said metal adsorbing CO ₂ - Preparation of an organic framework material of Bi-BTC, wherein said _{_{Bi (N0 3) 3 * 5H}} 2 0 and H ₃

The molar ratio of BTC is [1~3]: 3.

[Claim 6] a metal-organic framework material Bi-BTC adsorbing CO ₂ , obtained by the following method: Bi(NO ₃ ) 3-5H ₂ 0 is dissolved in a first solvent to form a solution A;

The solution B is slowly added to the solution A at room temperature to obtain a mixed solution; the mixed solution is crystallized at 120 ° C to 130 ° C for 2 to 3 days to obtain a first solid product; After the solid product is washed with an alcohol solution, it is placed in a drying oven at 110 ° C to 130 ° C to maintain 101! ~ 16h, that's it.

[Claim 7] - species of CO ₂ adsorption of the metal of the claims 6 - Bi-BTC organic framework material modification method, comprising the steps of:

Taking the reaction amount of the organic amine dissolved in the third solvent to form a solution C;

Adding adsorbed CO _{2 to} solution C

Metal-organic framework material Bi-BTC, turbid liquid D;

The turbid liquid D is refluxed at 80 ° C ~ 100 ° C 81! ~ 10h, a second solid product is obtained, and the second solid product is subjected to rotary evaporation to remove the solvent, and the obtained solid is placed in a drying oven at 80 ° C to 100 ° C to maintain 81! ~10h, the modified material Am/Bi-BTC was obtained.

[Claim 8] The modification method according to claim 7, wherein the organic amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polyethyleneimine.

[Claim 9] The modification method according to claim 7, wherein the third solvent is deionized water, methanol or absolute ethanol.

[Claim 10] The modification method according to claim 7, wherein a mass ratio of the reaction amount of the organic amine to Bi-BTC is 1: [6 to 1].