CN114618444B - Modified metal organic polyhedral material, preparation method and application thereof - Google Patents

Modified metal organic polyhedral material, preparation method and application thereof Download PDF

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CN114618444B
CN114618444B CN202111541052.6A CN202111541052A CN114618444B CN 114618444 B CN114618444 B CN 114618444B CN 202111541052 A CN202111541052 A CN 202111541052A CN 114618444 B CN114618444 B CN 114618444B
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cyclodextrin
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刘晓勤
顾宇阳
刘国良
孙林兵
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Nanjing Tech University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract

The invention discloses a preparation method of a modified metal-organic polyhedral material, which is simple and easy to implement, and the prepared beta-cyclodextrin and metal-organic polyhedral composite material can be freely assembled under the ultraviolet light/visible light switching, is convenient for regeneration circulation, and can still keep higher adsorption capacity for carbon dioxide after the regeneration circulation. The preparation method of the modified metal-organic polyhedral material comprises the step of coating beta-cyclodextrin on a metal-organic polyhedral side chain by utilizing weak interaction of a host and a guest through a pre-modification or post-modification method to form a highly dispersed porous composite material, namely the modified metal-organic polyhedral material.

Description

Modified metal organic polyhedral material, preparation method and application thereof
Technical Field
The invention relates to a metal-organic polyhedral material, a preparation method and application thereof, in particular to a modified metal-organic polyhedral material, a preparation method and application thereof.
Background
Climate change caused by greenhouse gases is still one of the most challenging and urgent environmental problems in the world today. Wherein CO 2 The influence on the environment and climate is the greatest, and the contribution value of the greenhouse effect is more than 55%. The original greenhouse effect is a natural phenomenon, and can reduce the temperature difference between day and night of the earth, thereby providing a proper environment for living on the earth. However, since the industrial revolution, the use of large amounts of fossil fuels has brought about a series of negative effects while promoting the rapid development of socioeconomic performance. For example, artificial CO 2 Excessive emission of gas seriously damages the stability of natural carbon circulation, and aggravates greenhouse effect, and the direct consequence is that glaciers near the north and south poles melt, sea level rises, numerous islands and low-lying coastal areas are threatened by being submerged and eroded by seawater, and inland areas are half desertified due to serious water shortage. Meanwhile, the aggravation of the greenhouse effect causes the continuous rise of the global air temperature, and a series of natural disasters (abnormal climate, frequent extreme weather, storm in winter, etc.) are caused. Therefore, it is imperative to slow down the greenhouse effect. Under the background, the green house gas is reduced in global agreement mode in each country of the world in 2015, and in additionThe foreign china also announced that carbon peaks were achieved before 2030 and carbon neutralization was achieved before 2060. It is therefore important to find a rational way to reduce the carbon dioxide content in current research.
The carbon dioxide capturing method commonly used at present is a chemical absorption method and an adsorption method. The chemical absorption method uses chemical solvent and CO 2 A reversible chemical reaction occurs to achieve the purpose of absorbing and desorbing carbon dioxide, so that a qualified absorbent is particularly important. At present, the alcohol amine method is mostly adopted in industry to trap CO 2 Amino groups in alcohol amines (primary amine, secondary amine) with CO 2 The reaction generates zwitterionic and then further reacts with the alcohol amine solution to generate carbamate. The alcohol amine absorbent has the function of absorbing CO 2 The advantages of high speed, large load, low price and the like are realized, and the method is widely applied to industry. However, alcohol amine method has the defects, and CO is desorbed 2 The energy consumption of the catalyst accounts for 70% -80% of the total energy consumption of trapping, and the desorption accounts for more than 60% of the total carbon trapping and sealing cost. The adsorption method is to utilize solid adsorbent to adsorb CO in the mixed gas 2 Is then subjected to CO under specific conditions 2 Desorbing and concentrating. Porous solid adsorption materials are widely concerned because of their abundant pore channels and easy regeneration. Wherein the Metal Organic Polyhedra (MOPs) are zero-dimensional and highly ordered molecules, and are formed by self-assembly of metal ions and organic ligands through coordination. MOPs are of a wide variety, are simple to synthesize and are easy to manipulate. Because of its size-adjustable cavity structure, the active sites are abundant, and attention has been paid in recent years to the fields of adsorption, catalysis and the like. Most Metal Organic Polyhedra (MOPs) are self-assembled from secondary building blocks of organic carboxylic acid/pyridine/pyrimidine ligands and transition metals. The metal coordination unsaturated sites on the framework and carbon dioxide molecules are easy to generate dipole strong interaction, so that the selective capture of carbon dioxide is shown, and the carbon dioxide adsorbent is widely applied to the field of carbon dioxide adsorption in recent years. However, MOPs tend to densely pack upon activation treatment to remove solvent molecules, thereby causing blocking of the active sites. This disadvantage severely limits the use of MOPs as adsorbents in carbon dioxide adsorptive separations. Thus, the MOPs are easy to processThe introduction of host-guest interactions to enhance the dispersibility of host MOPs by guest molecules is expected to solve the above-mentioned problems. In addition, the host-guest interaction is a process that the host and the guest are selectively combined to form a supermolecule with a specific function through non-covalent interaction under the conditions of structural complementation, energy matching and the like. Non-covalent interactions, including van der Waals forces, electrostatic attraction, hydrophobic interactions, hydrogen bonding, and the like, are key to generating host-guest recognition. Azobenzene is generally present as a guest in a multicomponent self-assembly process, and the multicomponent self-assembled macrocyclic bodies generally include crown ethers, cyclodextrins, calixarenes, cucurbiturils, and calixarenes. The supermolecular material prepared by the method overcomes the defects of raw materials by changing the hydrophilicity and hydrophobicity and stacking structural characteristics, and has wide application in the fields of biological materials, drug delivery, adsorption separation and the like.
Disclosure of Invention
The invention aims to provide a modified metal-organic polyhedral material, which overcomes the defect that active sites are blocked due to accumulation after activation of copper-based metal-organic polyhedral materials are commonly used.
The invention also aims to provide a preparation method of the modified metal-organic polyhedral material, which is simple and easy to implement, and the prepared beta-cyclodextrin and metal-organic polyhedral composite material can be freely assembled under the ultraviolet light/visible light switching, is convenient for regeneration circulation, and can still keep higher adsorption quantity for carbon dioxide after the regeneration circulation. .
The invention also provides application of the modified metal organic polyhedral material in separating carbon dioxide.
The aim of the invention is realized by the following technical scheme:
the preparation method of the modified metal-organic polyhedral material comprises the step of coating beta-cyclodextrin on a metal-organic polyhedral side chain by utilizing weak interaction of a host and a guest through a pre-modification or post-modification method to form a highly dispersed porous composite material, namely the modified metal-organic polyhedral material.
The preparation method of the modified metal organic polyhedron material has the further technical scheme that the metal organic polyhedron is a copper-based metal organic polyhedron, and is formed by self-assembly of cupric salt and 5-methyl azo phenyl isophthalic acid through coordination; the beta-cyclodextrin is coated on the side chain of the metal organic polyhedron, and the coating/desorption of the beta-cyclodextrin on the outer chain of the metal organic polyhedron is realized by ultraviolet light or visible light.
The preparation method of the modified metal organic polyhedral material can also adopt the further technical scheme that the pre-modification method comprises the steps of coating beta-cyclodextrin and azobenzene to form a compound by using solvent induction, and then adding cupric salt to prepare the modified metal organic polyhedral material. The further technical scheme is that the preparation method comprises the following steps:
1) Adding N, N-dimethylacetamide into 5-methyl azo phenyl isophthalic acid and performing ultrasonic treatment to obtain orange-red clear and transparent solution, and adding excessive beta-cyclodextrin into the orange-red clear and transparent solution for ultrasonic treatment until cyclodextrin is completely dissolved;
2) Dissolving copper acetate monohydrate in N, N-dimethylacetamide, carrying out ultrasonic treatment until the copper acetate monohydrate is fully dissolved to be clear and transparent, dropwise adding the copper acetate monohydrate into the solution in the step 1), continuing ultrasonic treatment to obtain a dark green solution, and standing and reacting the dark green solution in a dark dry place for more than two days;
3) And after the reaction is finished, adding absolute methanol, centrifuging to separate out green solid, washing with the absolute methanol for more than two times, and drying in vacuum to obtain green powder, namely the modified metal-organic polyhedral material prepared by the pre-modification method.
The preparation method of the modified metal organic polyhedral material can also adopt a further technical scheme that the post-modification method comprises the steps of self-assembling cupric salt and 5-methyl azo phenyl isophthalic acid to form copper-based metal organic polyhedral, and dispersing the copper-based metal organic polyhedral material in beta-cyclodextrin solutions with different concentrations to prepare the modified metal organic polyhedral material. The further technical scheme is that the preparation method comprises the following steps:
1) Adding N, N-dimethylacetamide into 5-methylazophenyl isophthalic acid and performing ultrasonic treatment to obtain orange-red clear and transparent solution;
2) Dissolving copper acetate monohydrate in N, N-dimethylacetamide, carrying out ultrasonic treatment until the copper acetate monohydrate is fully dissolved to be clear and transparent, dropwise adding the copper acetate monohydrate into the solution in the step 1), continuing ultrasonic treatment to obtain a dark green solution, and standing and reacting the dark green solution in a dark dry place for more than two days;
3) After the reaction is finished, adding absolute methanol, centrifuging to separate out green solid, washing with the absolute methanol for more than two times, and then drying in vacuum to obtain green powder, namely the metal organic polyhedral material;
4) Dispersing the metal organic polyhedral material obtained in the step 3) in N, N-dimethylformamide, adding beta-cyclodextrin, stirring for more than 12 hours in a dark place, centrifuging and drying to obtain green powder, namely the modified metal organic polyhedral material prepared by adopting a post-modification method.
According to the preparation method of the modified metal-organic polyhedral material, the further technical scheme can be that the molar ratio of the metal-organic polyhedral material to the beta-cyclodextrin is 2:1-1:2; the molar ratio of the metallo-organic polyhedra to the beta-cyclodextrin is preferably in the range of 1:1 to 1:2.
The preparation method of the modified metal-organic polyhedral material can be applied to separating carbon dioxide.
The application of the modified metal organic polyhedral material in separating carbon dioxide comprises the following steps: the modified metal organic polyhedral material is subjected to activation treatment and then is used for carbon dioxide adsorption/desorption, wherein the activation treatment is carried out at 70-100 ℃ and vacuum drying is carried out for more than 4 hours.
Compared with the prior art, the invention has the following beneficial effects:
in the present invention, the cyclodextrin has a cyclic structure, and the outside of the cavity is strongly polarized due to the hydroxyl group, while the inside is nonpolar, which also makes the cyclodextrin molecule suitable as a supramolecular host for coating the guest azobenzene molecule. The invention creatively utilizes the weak interaction of the host and the guest to directly coat the beta-cyclodextrin outside the copper-based metal organic polyhedral side chain to prepare the modified material, and the preparation method is simple and convenient and is easy to recycle. Meanwhile, the large-ring structure of the cyclodextrin gives higher stability to the flexible azo phenyl group on the side chain, increases the steric hindrance between the metal organic polyhedra and improves the dispersibility, and solves the problem that the metal organic polyhedra is easy to gather after being activated. The self-assembly process of the host and the guest is controlled reversibly under the ultraviolet light/visible light switching, so that the regeneration process of the material and the convenience thereof are realized. The modified metal organic polyhedral material prepared by the invention can be used as a carbon dioxide adsorbent, the adsorption gain rate of the carbon dioxide adsorbent on carbon dioxide can be up to 153%, and the gas adsorption selectivity gain rate of carbon dioxide/nitrogen can be up to 138%. Meanwhile, based on the principle of weak interaction between a host and a guest, the invention is not limited to the copper-based metal-organic polyhedron, can be theoretically expanded to the whole metal-organic polyhedron field (such as Zr, pd and Rh-based metal-organic polyhedron), and the azobenzene guest molecule on the outer chain can also interact with other annular structures such as crown ether, calixarene, cucurbituril and pillared arene to form a supermolecule material, so that the problems of poor stability and easy accumulation commonly existing in MOPs are overcome, and the efficient modification of the material is realized.
Detailed Description
The present invention is described below by way of specific examples, but the present invention is not limited to the following examples, and modifications are included in the technical scope of the present invention without departing from the spirit and scope of the present invention.
In the invention, the main guest action test steps are as follows: the cyclodextrin cage is strongly polarized on the outside due to the presence of hydroxyl functions, while the inside is nonpolar. This also makes cyclodextrin molecules suitable as a supramolecular host for coating azobenzene molecules. Dispersing ligand and metal organic polyhedral material in N, N-dimethylformamide solution, sucking 3mL of sample in a quartz cuvette, testing the absorbance of the sample at 320nm nearby by an ultraviolet-visible spectrophotometer, adding excessive cyclodextrin into the quartz cuvette, and slightly increasing the absorbance at 320nm nearby if the ligand and the metal organic polyhedral material self-assemble to form inclusion compound.
The light response test steps are as follows: the material has an azo phenyl group on the outer chain, and can generate cis-trans isomerism under the alternate irradiation of ultraviolet light/visible light. After ultraviolet irradiation, the azo phenyl group is in a stable cis-cis state, and cyclodextrin molecules coated on the metal organic polyhedron fall off at the moment; after irradiation by visible light, the azo phenyl group is in a stable trans-trans state, at the moment, the metal organic polyhedron is self-assembled with cyclodextrin molecules again, and the two states are tested by an ultraviolet-visible spectrophotometer.
The gas adsorption experimental steps are as follows: 0.05g of the dried sample was placed in an ASAP 2020 full-automatic rapid surface area and porosity analyzer for analysis. The pretreatment temperature of the copper-based metal-organic polyhedral material is 60 DEG C ℃ The pretreatment time was 6h. The activation treatment temperature of the modified metal organic polyhedral material is 80 ℃, and the pretreatment time is 4 hours.
Example 1
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; adding excessive beta-cyclodextrin into the solution, and performing ultrasonic treatment for 10min until the cyclodextrin is completely dissolved; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, ultrasonic treatment is continued for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, adding 20mL of absolute methanol into a glass bottle, centrifuging to separate out green solid, washing twice by using the absolute methanol, and then drying at 60 ℃ in vacuum for 4 hours to obtain green powder, namely the copper-based metal organic polyhedral modified material prepared by a pre-modification strategy.
Light response test: dispersing the prepared modified metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
And (3) master-client action test: dissolving ligand 5-methyl azo phenyl isophthalic acid in N, N-dimethylformamide, diluting to a proper concentration, placing the mixture into a 3mL quartz cuvette, testing the absorbance of a sample by using an ultraviolet-visible spectrophotometer, adding excessive beta-cyclodextrin, standing for 2 hours after the mixture is completely dissolved in the cuvette, testing the absorbance, and slightly rising the absorbance in a 320nm wave band to prove that an azobenzene molecule and the beta-cyclodextrin form an inclusion compound.
Gas adsorption test: the adsorption amount of carbon dioxide at 0 ℃ of the modified metal organic polyhedron obtained by the pre-modification strategy is 38mL/g, and the adsorption amount of nitrogen is 3mL/g.
Example 2
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, the solution is continuously subjected to ultrasonic treatment for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, 20mL of absolute methanol is added into a glass bottle, the absolute methanol is used for centrifugal separation, the green solid is washed twice, and then the green powder is obtained after vacuum drying for 4 hours at 60 ℃ after the absolute methanol is used for washing, and the light response copper-based metal organic polyhedron is obtained. Dispersing the obtained metal organic polyhedron in 20mL of N, N-dimethylformamide, adding a proper amount of beta-cyclodextrin according to the molar ratio of the metal organic polyhedron to the beta-cyclodextrin of 2:1, stirring for 12 hours in a dark place, centrifuging and drying to obtain green powder, namely the metal organic polyhedron modified material prepared by adopting a post-modification strategy.
Light response test: dispersing the prepared modified metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
And (3) master-client action test: dispersing the prepared metal organic polyhedral modified material in N, N-dimethylformamide, diluting to a proper concentration, placing the diluted material in a 3mL quartz cuvette, testing the absorbance of a sample by using an ultraviolet-visible spectrophotometer, adding excessive beta-cyclodextrin, standing for 2 hours after the beta-cyclodextrin is completely dissolved in the cuvette, testing the absorbance, and slightly rising the absorbance by 0.02 in a 320nm wave band to prove that an azobenzene molecule and the beta-cyclodextrin form an inclusion compound.
Gas adsorption test: the adsorption amount of carbon dioxide at 0 ℃ of the modified metal organic polyhedron obtained by the post-modification strategy is 24mL/g, and the adsorption amount of nitrogen is 2mL/g.
Example 3
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, the solution is continuously subjected to ultrasonic treatment for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, 20mL of absolute methanol is added into a glass bottle, the absolute methanol is used for centrifugal separation, the green solid is washed twice, and then the green powder is obtained after vacuum drying for 4 hours at 60 ℃ after the absolute methanol is used for washing, and the light response copper-based metal organic polyhedron is obtained. Dispersing the obtained metal organic polyhedron in 20mL of N, N-dimethylformamide, adding a proper amount of beta-cyclodextrin according to the molar ratio of the metal organic polyhedron to the beta-cyclodextrin of 3:2, stirring for 12 hours in a dark place, centrifuging and drying to obtain green powder, namely the metal organic polyhedron modified material prepared by adopting a post-modification strategy.
Light response test: dispersing the prepared modified metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
And (3) master-client action test: dispersing the prepared metal organic polyhedral modified material in N, N-dimethylformamide, diluting to a proper concentration, placing the diluted material in a 3mL quartz cuvette, testing the absorbance of a sample by using an ultraviolet-visible spectrophotometer, adding excessive beta-cyclodextrin, standing for 2 hours after the beta-cyclodextrin is completely dissolved in the cuvette, testing the absorbance, and slightly rising the absorbance at a 320nm wave band by 0.03 to prove that an azobenzene molecule and the beta-cyclodextrin form an inclusion compound.
Gas adsorption test: the modified metal-organic polyhedron obtained by the post-modification strategy has an adsorption amount of 29mL/g for carbon dioxide and 3mL/g for nitrogen at 0 ℃.
Example 4
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, the solution is continuously subjected to ultrasonic treatment for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, 20mL of absolute methanol is added into a glass bottle, the absolute methanol is used for centrifugal separation, the green solid is washed twice, and then the green powder is obtained after vacuum drying for 4 hours at 60 ℃ after the absolute methanol is used for washing, and the light response copper-based metal organic polyhedron is obtained. Dispersing the obtained metal organic polyhedron in 20mL of N, N-dimethylformamide, adding a proper amount of beta-cyclodextrin according to the molar ratio of the metal organic polyhedron to the beta-cyclodextrin of 1:1, stirring for 12 hours in a dark place, centrifuging and drying to obtain green powder, namely the metal organic polyhedron modified material prepared by adopting a post-modification strategy.
Light response test: dispersing the prepared modified metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
And (3) master-client action test: dispersing the prepared metal organic polyhedral modified material in N, N-dimethylformamide, diluting to a proper concentration, placing the diluted material in a 3mL quartz cuvette, testing the absorbance of a sample by using an ultraviolet-visible spectrophotometer, adding excessive beta-cyclodextrin, standing for 2 hours after the beta-cyclodextrin is completely dissolved in the cuvette, testing the absorbance, and slightly rising the absorbance at a 320nm wave band by 0.03 to prove that an azobenzene molecule and the beta-cyclodextrin form an inclusion compound.
Gas adsorption test: the modified metal-organic polyhedron obtained by the post-modification strategy has an adsorption amount of 33mL/g for carbon dioxide and 3mL/g for nitrogen at 0 ℃.
Example 5
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, the solution is continuously subjected to ultrasonic treatment for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, 20mL of absolute methanol is added into a glass bottle, the absolute methanol is used for centrifugal separation, the green solid is washed twice, and then the green powder is obtained after vacuum drying for 4 hours at 60 ℃ after the absolute methanol is used for washing, and the light response copper-based metal organic polyhedron is obtained. Dispersing the obtained metal organic polyhedron in 20mL of N, N-dimethylformamide, adding a proper amount of beta-cyclodextrin according to the molar ratio of the metal organic polyhedron to the beta-cyclodextrin of 2:3, stirring for 12 hours in a dark place, centrifuging and drying to obtain green powder, namely the metal organic polyhedron modified material prepared by adopting a post-modification strategy.
Light response test: dispersing the prepared modified metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
And (3) master-client action test: dispersing the prepared metallo-organic polyhedral modified material in N, N-dimethylformamide, diluting to a proper concentration, placing the mixture in a 3mL quartz cuvette, testing the absorbance of a sample by using an ultraviolet-visible spectrophotometer, adding excessive beta-cyclodextrin, standing for 2 hours after the mixture is completely dissolved in the cuvette, testing the absorbance, slightly increasing the absorbance at a wave band of 320nm by 0.03, and proving that an azobenzene molecule and the beta-cyclodextrin form an inclusion compound.
Gas adsorption test: the adsorption amount of carbon dioxide at 0 ℃ of the modified metal organic polyhedron obtained by the post-modification strategy is 32mL/g, and the adsorption amount of nitrogen is 3mL/g.
Example 6
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, the solution is continuously subjected to ultrasonic treatment for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, 20mL of absolute methanol is added into a glass bottle, the absolute methanol is used for centrifugal separation, the green solid is washed twice, and then the green powder is obtained after vacuum drying for 4 hours at 60 ℃ after the absolute methanol is used for washing, and the light response copper-based metal organic polyhedron is obtained. Dispersing the obtained metal organic polyhedron in 20mL of N, N-dimethylformamide, adding a proper amount of beta-cyclodextrin according to the molar ratio of the metal organic polyhedron to the beta-cyclodextrin of 1:2, stirring for 12 hours in a dark place, centrifuging and drying to obtain green powder, namely the metal organic polyhedron modified material prepared by adopting a post-modification strategy.
Light response test: dispersing the prepared modified metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
And (3) master-client action test: dispersing the prepared metallo-organic polyhedral modified material in N, N-dimethylformamide, diluting to a proper concentration, placing the mixture in a 3mL quartz cuvette, testing the absorbance of a sample by using an ultraviolet-visible spectrophotometer, adding excessive beta-cyclodextrin, standing for 2 hours after the mixture is completely dissolved in the cuvette, testing the absorbance, slightly increasing the absorbance at a wave band of 320nm by 0.03, and proving that an azobenzene molecule and the beta-cyclodextrin form an inclusion compound.
Gas adsorption test: the adsorption amount of carbon dioxide at 0 ℃ of the modified metal organic polyhedron obtained by the post-modification strategy is 28mL/g, and the adsorption amount of nitrogen is 2mL/g.
Comparative example 1
60mg of 5-methyl azo phenyl isophthalic acid is weighed into a 50mL glass bottle, 10mL of N, N-dimethyl formamide is added, and ultrasonic treatment is carried out for 5min to obtain orange red clear and transparent solution; 40mg of copper acetate monohydrate is weighed and dissolved in 10mL of N, N-dimethylacetamide, after the copper acetate monohydrate is fully dissolved to be clear and transparent by ultrasonic treatment for 10min, the copper acetate monohydrate is dropwise added into a 50mL glass bottle, the solution is continuously subjected to ultrasonic treatment for 10min to obtain a dark green solution, and the glass bottle is placed in a dark dry place for standing reaction for two days. After the reaction is finished, 20mL of absolute methanol is added into a glass bottle, the absolute methanol is used for centrifugal separation, the green solid is washed twice, and then the green powder is obtained after vacuum drying for 4 hours at 60 ℃ after the absolute methanol is used for washing, and the light response copper-based metal organic polyhedron is obtained.
Light response test: dispersing the prepared metal organic polyhedron in N, N-dimethylformamide, sucking 3mL of sample, placing the sample in a quartz cuvette, and testing the absorbance of the sample in the wave band of 300-700nm by an ultraviolet-visible spectrophotometer. After 30s of ultraviolet irradiation, absorbance was continuously measured, and the 320nm absorption band was found to decrease and the 450nm absorption band was found to increase. After irradiation with visible light for 30 seconds, absorbance was continuously measured, and the absorption band at 320nm was found to be increased and the absorption band at 450nm was found to be decreased. Thereby proving the rapid photo-responsiveness of the material.
Gas adsorption test: the adsorption amount of carbon dioxide of the metal-organic polyhedron at 0 ℃ is 15mL/g, and the adsorption amount of nitrogen gas is 2mL/g.
Application examples
The materials in examples 1 to 6 and comparative example 1 were subjected to activation treatment using an ASAP 2020 full-automatic rapid surface area and porosity analyzer using the adsorption performance of the metal-organic polyhedron and the modified metal-organic polyhedron materials prepared as described above to carbon dioxide. Accurately weighing 0.05g of sample in a quartz tube, and measuring the temperature to 273K. And the carbon dioxide/nitrogen gas adsorption selectivity was calculated by means of the IAST model.
The above specific examples are provided to make the above objects, features and advantages of the present invention more comprehensible, and the present invention includes but is not limited to the above specific examples. The data for the tests of examples 1-6 and comparative example 1 are shown in Table 1.
Table 1 gas adsorption behavior and gain ratio of the modified materials in examples 1 to 6
According to the comparison of the data in the table 1, the invention can overcome the defect that the original photoresponsive copper-based metal organic polyhedron is activated to cause molecular aggregation to block bivalent copper active sites on a binuclear copper secondary building unit, the dispersibility and the stability of the prepared composite material are further improved, the adsorption capacity of the material to carbon dioxide is greatly increased, and compared with the raw materials, the maximum gain rate of the adsorption capacity of the modified material prepared directly by the front modification method can reach 153%, and the gas adsorption selectivity gain rate of carbon dioxide/nitrogen can reach 138%.

Claims (7)

1. A preparation method of a modified metal-organic polyhedral material is characterized in that the preparation method utilizes the interaction of main and guest bodies to coat beta-cyclodextrin on a side chain of the metal-organic polyhedral material by a pre-modification or post-modification method, so as to form a highly dispersed porous composite material, namely the modified metal-organic polyhedral material; the metal organic polyhedron is a copper-based metal organic polyhedron and is formed by self-assembly of divalent copper salt and 5-methyl azo phenyl isophthalic acid through coordination; the beta-cyclodextrin is coated on the metal organic polyhedral side chain, and the beta-cyclodextrin is coated on the metal organic polyhedral side chain by ultraviolet light or visible light; the pre-modification method comprises the steps of coating beta-cyclodextrin and 5-methyl azo phenyl isophthalic acid to form a compound by utilizing solvent induction, and adding cupric salt to prepare a modified metal organic polyhedral modifying material; the post-modification method is to self-assemble the cupric salt and the 5-methyl azo phenyl isophthalic acid to form copper-based metal organic polyhedron, and then disperse the copper-based metal organic polyhedron in beta-cyclodextrin solutions with different concentrations to prepare the modified metal organic polyhedron modified material.
2. The method of manufacturing according to claim 1, comprising the steps of:
1) Adding N, N-dimethylacetamide into 5-methyl azo phenyl isophthalic acid and performing ultrasonic treatment to obtain orange-red clear and transparent solution, and adding excessive beta-cyclodextrin into the orange-red clear and transparent solution for ultrasonic treatment until the cyclodextrin is completely dissolved;
2) Dissolving copper acetate monohydrate in N, N-dimethylacetamide, carrying out ultrasonic treatment until the copper acetate monohydrate is fully dissolved to be clear and transparent, dropwise adding the copper acetate monohydrate into the solution in the step 1), continuing ultrasonic treatment to obtain a dark green solution, and standing and reacting the dark green solution in a dark dry place for more than two days;
3) And after the reaction is finished, adding absolute methanol, centrifuging to separate out green solid, washing with the absolute methanol for more than two times, and then drying in vacuum to obtain green powder, namely the modified metal-organic polyhedral material prepared by the pre-modification method.
3. The method of manufacturing according to claim 1, comprising the steps of:
1) Adding N, N-dimethylacetamide into 5-methylazophenyl isophthalic acid and performing ultrasonic treatment to obtain orange-red clear and transparent solution;
2) Dissolving copper acetate monohydrate in N, N-dimethylacetamide, carrying out ultrasonic treatment until the copper acetate monohydrate is fully dissolved to be clear and transparent, dropwise adding the copper acetate monohydrate into the solution in the step 1), continuing ultrasonic treatment to obtain a dark green solution, and standing and reacting the dark green solution in a dark dry place for more than two days;
3) After the reaction is finished, adding absolute methanol, centrifuging to separate out green solid, washing with the absolute methanol for more than two times, and then vacuum drying to obtain green powder, namely the metal organic polyhedral material;
4) Dispersing the metal organic polyhedral material obtained in the step 3) in N, N-dimethylformamide, adding beta-cyclodextrin, stirring in a dark place for more than 12 and h, centrifuging and drying to obtain green powder, namely the modified metal organic polyhedral material prepared by adopting a post-modification method.
4. The method of claim 1, wherein the molar ratio of the metallo-organic polyhedra to the beta-cyclodextrin is from 2:1 to 1:2.
5. A modified metallo-organic polyhedral material prepared by the method of any one of claims 1-4.
6. Use of the modified metallo-organic polyhedral material according to claim 5 for separating carbon dioxide.
7. Use of a modified metallo-organic polyhedral material according to claim 6 for separating carbon dioxide, comprising the steps of: the modified metal organic polyhedral material is subjected to activation treatment and then is used for carbon dioxide adsorption/desorption, wherein the activation treatment is carried out at 70-100 ℃ and vacuum drying is carried out for more than 3 hours.
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CN111443117A (en) * 2020-03-12 2020-07-24 济南大学 Preparation method and application of bimanual β -CD @ Cu-MOF nano composite sensor
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