CN113651969A - Metal-organic framework material modified by organic amine cations and preparation method thereof - Google Patents
Metal-organic framework material modified by organic amine cations and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of an organic amine cation modified metal-organic framework material, which adopts carboxylic acid organic ligand modified by functional groups, amide organic solvent and transition metal ions as reactants, adds a certain amount of acid regulator, and reacts at a certain temperature to obtain the organic amine cation modified metal-organic framework material. The organic amine cation modified metal-organic framework material prepared by the method provided by the invention is used for separating carbon dioxide, can obviously improve the acting force between carbon dioxide molecules and pore channels, and improves the separation performance of the carbon dioxide. The invention also provides an organic amine cation modified metal-organic framework material.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to an organic amine cation modified metal-organic framework material and a preparation method thereof.
Background
The metal-organic framework (MOF) material is a crystalline porous material which develops most rapidly in recent 20 years, is an organic-inorganic hybrid framework material formed by coordination and self-assembly of organic ligands and metal ions, has the advantages of uniform pore structure, high specific surface area, modifiable pore structure and pore chemical environment and the like, and has wide application prospects in multiple fields of gas storage and separation, catalysis, sensing, drug transmission and the like. In particular, in the field of gas separation, the structural designability and tunability of metal-organic framework materials endow the metal-organic framework materials with special adsorption and separation properties, and the metal-organic framework materials are considered to be gas separation adsorbents with bright application prospects.
Since carbon dioxide is the main substance causing greenhouse effect, the separation of carbon dioxide from mixed gases is of great significance for reducing carbon emissions. The metal-organic framework material has important application prospect in the field of carbon dioxide separation. Due to the acidity of carbon dioxide molecules, molecules containing basic groups, such as organic amine, can be modified inside the pore channels of the metal-organic framework material by adjusting, so that the adsorption selectivity of the carbon dioxide can be improved. However, most of the conventional methods for modifying basic groups adopt post-modification methods, i.e. organic amines are modified inside the metal-organic framework by means of impregnation and the like. However, most organic amines have a certain damage to the framework of the metal-organic framework material, so that the method has a large limitation.
Disclosure of Invention
In view of the above, aiming at the defects of the existing metal-organic framework material in the method for modifying basic functional groups, the invention provides a novel method for modifying basic groups, organic amine cations are generated in situ in the metal-organic framework material by regulating and controlling synthesis conditions, and the metal-organic framework material modified by the organic amine cations prepared by the method provided by the invention can solve the problem of skeleton damage of the organic amine to the metal-organic framework material in a post-modification method and simultaneously shows excellent carbon dioxide separation performance.
The invention provides a preparation method of an organic amine cation modified metal-organic framework material, which comprises the following steps:
mixing an organic ligand and a metal ion compound in a solvent and a regulator to obtain a mixture;
and reacting the mixture to obtain the organic amine cation modified metal-organic framework material.
Preferably, the organic ligand is a carboxylic acid ligand containing a functional group.
Preferably, the number of carbon chains of the functional group is 1 to 3.
Preferably, the organic ligand is selected from one or more of 1,3, 5-tri (3, 5-dicarboxyphenyl) -2,4, 6-trimethoxybenzene, 1,3, 5-tri (3, 5-dicarboxyphenyl) -2,4, 6-trihydroxybenzene and 1,3, 5-tri (3, 5-dicarboxyphenyl) -2,4, 6-trimethylbenzene.
Preferably, the metal ion compound is a transition metal ion compound.
Preferably, the molar ratio of the organic ligand to the metal ion compound is 1: (0.5-2).
Preferably, the solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide.
Preferably, the modifier is an acid.
Preferably, the reaction temperature is 60-150 ℃.
The invention provides an organic amine cation modified metal-organic framework material prepared by the method in the technical scheme.
The metal-organic framework material modified by the organic amine cations prepared by the invention is an anion framework, the organic amine ions in the pore channels are cations, and the whole metal-organic framework material is electrically neutral through charge balance between the cations and the anion framework.
In the invention, the organic amine solvent is decomposed, and organic amine cations are generated in situ in the metal-organic framework material in the pore channel.
According to the invention, the organic solvent containing the amide group can be decomposed under the heating condition to generate the organic amine, the organic solvent can play a role of a template agent in the formation process of the metal-organic framework material, and a product of the organic solvent after decomposition can stay in a pore channel of the metal-organic framework material, so that the metal-organic framework material modified by the organic amine cation is formed. The organic amine group is generated in situ in the process of forming the metal-organic framework material, so that the framework of the metal-organic framework material cannot be damaged. In addition, due to the action of charge balance, organic amine cations are uniformly distributed in the pores of the metal-organic framework material and do not aggregate in the pores.
The invention provides an organic amine cation modified metal-organic framework material, which takes the metal-organic framework material as a material for separating carbon dioxide, and has important significance for improving the adsorption separation property of the carbon dioxide and improving the carbon dioxide separation performance of the metal-organic framework material; the organic functional group on the organic ligand has important influence on the adjustment of the topological structure of the metal-organic framework material; the spatial configuration of the organic ligand in the metal-organic framework material can be changed by modifying functional groups on the organic ligand; these different spatial configurations are of great importance for obtaining metal-organic framework materials with specific configurations; according to the invention, organic amine cations can be generated in situ in the pore channel of the metal-organic framework material, so that the framework damage to the metal-organic framework material caused by a post-modification method is avoided, and meanwhile, the method also reduces the operation steps; the metal-organic framework material modified by the organic amine cations, which is prepared by the invention, has alkaline groups and unbalanced charges, so that the acting force between carbon dioxide molecules and the metal-organic framework material is greatly improved, the adsorption selectivity of the metal-organic framework material on carbon dioxide is obviously improved, and the carbon dioxide separation performance of the metal-organic framework material is improved.
Drawings
FIG. 1 is a crystal structure stacking diagram of an organic amine cation modified metal-organic framework material prepared in example 3 of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of the organic amine cation modified metal-organic framework material prepared in example 3 of the present invention;
FIG. 3 is an X-ray single crystal diffraction analysis chart of the organic amine cation modified metal-organic framework material prepared in example 3 of the present invention;
FIG. 4 is an X-ray powder diffraction pattern of the organic amine cation modified metal-organic framework material prepared in example 4 of the present invention;
FIG. 5 is an X-ray single crystal diffraction analysis chart of the organic amine cation modified metal-organic framework material prepared in example 5 of the present invention;
FIG. 6 is the adsorption isotherm of nitrogen gas for the organic amine cation-modified metal-organic framework material prepared in example 3 of the present invention;
FIG. 7 is the adsorption isotherm of nitrogen gas for the organic amine cation-modified metal-organic framework material prepared in example 4 of the present invention;
FIG. 8 is the adsorption isotherm of carbon dioxide by the organic amine cation-modified metal-organic framework material prepared in example 3 of the present invention;
FIG. 9 is the adsorption isotherm of hydrogen gas by the organic amine cation-modified metal-organic framework material prepared in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The invention provides a preparation method of an organic amine cation modified metal-organic framework material, which comprises the following steps:
mixing an organic ligand and a metal ion compound in a solvent and a regulator to obtain a mixture;
and reacting the mixture to obtain the organic amine cation modified metal-organic framework material.
In the present invention, the organic ligand is preferably a carboxylic acid ligand having a rigid structure and having a side chain organic functional group; the number of carbon chains of the organic functional group is preferably 1-3, and more preferably 2; the organic ligand is preferably selected from one or more of 1,3, 5-tri (3, 5-dicarboxyphenyl) -2,4, 6-trimethoxybenzene, 1,3, 5-tri (3, 5-dicarboxyphenyl) -2,4, 6-trihydroxybenzene and 1,3, 5-tri (3, 5-dicarboxyphenyl) -2,4, 6-trimethylbenzene.
In the present invention, the organic ligand preferably has the structure of formula I:
in the formula I, R is selected from-OCH3-OH or-CH3。
In the invention, the preparation method of the organic ligand comprises the following steps:
in the present invention, the preparation method of the organic ligand preferably includes:
adopting Suzuki coupling reaction synthesis, mixing a compound (functional group substituted bromobenzene) with a structure shown in a formula II with 3, 5-ethyl phthalate phenylboronic acid, and reacting in dioxane under the action of a catalyst and potassium phosphate to obtain an intermediate (ligand esterified substance);
putting the intermediate into a sodium hydroxide aqueous solution, adding a mixed solvent of ethanol and tetrahydrofuran, carrying out hydrolysis reaction, and then acidifying to obtain an organic ligand;
in the formula II, R is selected from-OCH3-OH or-CH3。
In the present invention, the method for preparing 3, 5-dicarboxylic acid ethyl ester phenylboronic acid preferably comprises:
3, 5-dicarboxyphenylboronic acid, ethanol and sulfuric acid are reacted, 3, 5-dicarboxylic acid ethyl ester phenylboronic acid.
In the present invention, the ethanol is preferably anhydrous ethanol.
In the present invention, the sulfuric acid is preferably concentrated sulfuric acid.
In the present invention, it is preferable to add concentrated sulfuric acid dropwise to carry out the reaction.
In the present invention, the reaction of 3, 5-dicarboxyphenylboronic acid, ethanol and sulfuric acid is preferably a heating reflux reaction; the reaction time is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours.
In the present invention, it is preferable that the reaction of 3, 5-dicarboxyphenylboronic acid, ethanol and sulfuric acid is completed by further comprising:
the obtained reaction product was concentrated under reduced pressure to remove ethanol.
In the present invention, it is preferable that the vacuum concentration further comprises:
adding the product after decompression concentration into sodium bicarbonate water solution for precipitation to obtain precipitate;
filtering, washing and drying the precipitate to obtain a dried product;
and dissolving the dried product, and then recrystallizing to obtain the 3, 5-ethyl diformate phenylboronic acid.
In the invention, the concentration of the sodium bicarbonate aqueous solution is preferably 8-12 mol/L, more preferably 9-11 mol/L, and most preferably 10 mol/L.
In the present invention, the precipitate is preferably a white floc.
In the present invention, the water washing is preferably water washing until the pH value is neutral.
In the invention, the drying temperature is preferably 50-70 ℃, more preferably 55-65 ℃, and most preferably 60 ℃; the drying time is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours.
In the present invention, the dissolution is preferably carried out in ethyl acetate.
In the invention, the molar ratio of the compound with the structure shown in the formula II to the 3, 5-ethyl phthalate phenylboronic acid is preferably 1 (2-4), more preferably 1 (2.5-3.5), and most preferably 1: 3.
In the present invention, the catalyst is preferably tetrakis (triphenylphosphine) palladium.
In the invention, the molar ratio of the structural compound of the formula II to the catalyst is preferably 1 (0.03-0.07), more preferably 1 (0.04-0.06), and most preferably 1: 0.05.
In the present invention, the potassium phosphate is preferably anhydrous potassium phosphate.
In the invention, the molar ratio of the compound with the structure shown in the formula II to potassium phosphate is preferably 1 (16-20), more preferably 1 (17-19), and most preferably 1: 18.
In the present invention, it is preferable that the reaction in dioxane further comprises: and removing oxygen.
In the invention, the temperature for the reaction in dioxane is preferably 80-100 ℃, more preferably 85-95 ℃, and most preferably 90 ℃; the reaction time is preferably 65 to 75 hours, more preferably 68 to 72 hours, and most preferably 70 hours.
In the present invention, it is preferable that the reaction in dioxane further comprises:
filtering the obtained reaction product, concentrating under reduced pressure, and extracting.
In the present invention, the concentration under reduced pressure is used to remove the solvent.
In the present invention, the extraction is preferably carried out by extracting the reaction product with chloroform.
In the present invention, it is preferable that the extraction further comprises:
concentrating the extracted extract under reduced pressure, performing column chromatography on the concentrated product in a silica gel column, and concentrating the eluent after the chromatography under reduced pressure to obtain an intermediate.
In the present invention, the concentration of the aqueous sodium hydroxide solution is preferably 3 to 5mol/L, more preferably 3.5 to 4.5mol/L, and most preferably 4 mol/L.
In the present invention, the hydrolysis reaction is preferably heated to reflux; the time of the hydrolysis reaction is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours.
In the present invention, the hydrolysis reaction process is preferably detected by thin layer chromatography.
In the present invention, it is preferable that the hydrolysis reaction further comprises:
and filtering and concentrating a reaction product obtained after the hydrolysis reaction.
In the present invention, the filtration is to remove insoluble matter; the concentration is performed to remove the organic solvent.
In the present invention, the acidification step preferably further comprises:
and diluting the product after the hydrolysis reaction and then cooling.
In the present invention, the diluted reagent is preferably water, more preferably distilled water.
In the invention, the temperature for reducing the temperature is preferably room temperature, more preferably 20-30 ℃, more preferably 22-28 ℃, and most preferably 24-26 ℃.
In the present invention, the acidifying agent is preferably hydrochloric acid, more preferably concentrated hydrochloric acid.
In the invention, concentrated hydrochloric acid is preferably dropwise added in the acidification process; in the acidification process, the pH is preferably adjusted to 2-4, more preferably 2.5-3.5, and most preferably 3.
In the present invention, it is preferable that a large amount of white precipitate is precipitated after the acidification is completed.
In the present invention, it is preferable that the acidification step further comprises:
and filtering, washing and drying the white precipitate obtained after acidification to obtain the white-like powdery organic ligand.
In the present invention, the washing is preferably performed with water, more preferably with distilled water; the number of washing is preferably 2 to 4, and more preferably 3.
In the invention, the drying temperature is preferably 50-70 ℃, more preferably 55-65 ℃, and most preferably 60 ℃; the drying time is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours.
In the present invention, the metal ionic compound is preferably a transition metal ionic compound, and the transition metal ion is preferably selected from cadmium (Cd)2+) Iron (Fe)2+) Cobalt (Co)2+) Nickel (Ni)2+) And zinc (Zn)2+) One or more of them.
In the present invention, the metal ion compound is preferably a soluble inorganic salt of the metal ion compound, and more preferably one or more of a nitrate, a sulfate, a perchlorate, and a fluoroborate of the metal ion compound. In the present invention, the metal ion compound is preferably selected from one or more of cadmium nitrate, cadmium sulfate, zinc nitrate, zinc sulfate, cobalt nitrate, nickel sulfate, ferrous sulfate, and the like.
In the present method, the molar ratio of the organic ligand to the metal ion compound is preferably 1: (0.5 to 2), more preferably 1: (1 to 1.5), and most preferably 1: (1.2-1.3).
In the present invention, the solvent is preferably one or more selected from the group consisting of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA), and N, N-Diethylformamide (DEF).
In the present invention, the modifier is an acid; the acid is preferably selected from one or more of hydrochloric acid, sulfuric acid and nitric acid, more preferably nitric acid, and most preferably concentrated nitric acid; the mass concentration of the concentrated nitric acid is preferably 65-70%, more preferably 66-69%, and most preferably 67-68%.
In the invention, the molar ratio of the regulator to the organic ligand is preferably (0.01-1): 1, more preferably (0.05 to 0.5): 1, more preferably (0.1 to 0.4): 1, most preferably (0.2 to 0.3): 1.
in the present invention, the mixing and reaction are preferably carried out in a hydrothermal reaction tank.
In the present invention, the organic ligand and the metal ion self-assemble to form the metal-organic framework compound in the reaction process.
In the invention, the temperature of the mixture for reaction is preferably 60-150 ℃, more preferably 60-110 ℃, more preferably 70-100 ℃, and most preferably 80-90 ℃; the reaction time is preferably 6 to 72 hours, more preferably 10 to 70 hours, more preferably 20 to 60 hours, more preferably 30 to 50 hours, and most preferably 40 hours.
In the present invention, the mixture preferably further comprises, after the reaction is completed:
and filtering, washing and drying the reaction product to obtain the organic amine cation modified metal-organic framework material.
In the invention, the filtering method is preferably vacuum filtration, and the vacuum degree in the filtration process is preferably 0.8-1.2 KPa, and more preferably 1 KPa.
In the present invention, the washing reagent is preferably selected from one or more organic solvents such as methanol, ethanol, acetone, dichloromethane, chloroform, etc.
In the invention, the drying temperature is preferably 60-130 ℃, more preferably 70-120 ℃, more preferably 80-110 ℃, and most preferably 90-100 ℃.
The invention provides an organic amine cation modified metal-organic framework material prepared by the method in the technical scheme.
In the invention, the metal-organic framework material is an anionic framework; the pore channels of the metal-organic framework material contain organic amine cations.
The invention provides an organic amine cation modified metal-organic framework material, which takes the metal-organic framework material as a material for separating carbon dioxide, and has important significance for improving the adsorption separation property of the carbon dioxide and improving the carbon dioxide separation performance of the metal-organic framework material; the organic functional group on the organic ligand has important influence on the adjustment of the topological structure of the metal-organic framework material; the spatial configuration of the organic ligand in the metal-organic framework material can be changed by modifying functional groups on the organic ligand; these different spatial configurations are of great importance for obtaining metal-organic framework materials with specific configurations; according to the invention, organic amine cations can be generated in situ in the pore channel of the metal-organic framework material, so that the framework damage to the metal-organic framework material caused by a post-modification method is avoided, and meanwhile, the method also reduces the operation steps; the metal-organic framework material modified by the organic amine cations, which is prepared by the invention, has alkaline groups and unbalanced charges, so that the acting force between carbon dioxide molecules and the metal-organic framework material is greatly improved, the adsorption selectivity of the metal-organic framework material on carbon dioxide is obviously improved, and the carbon dioxide separation performance of the metal-organic framework material is improved.
Example 1
1) 1,3, 5-trimethoxy-2, 4, 6-tribromobenzene (CAS:105404-90-8) (4.049g, 10mmol) and 3, 5-dicarboxylic acid ethyl ester benzeneboronic acid (8.780g, 33mmol) were added to a reaction flask, and 21.0g of anhydrous potassium phosphate was added. After removing oxygen from the reactor by vacuum line, tetrakis (triphenylphosphine) palladium (0.5g, 0.43mmol) was added, 300ml of deoxygenated dioxane was added, and the reaction was carried out at 90 ℃ for 72 hours. Then filtering, decompressing and concentrating to remove the solvent, and extracting the reaction product by trichloromethane. And concentrating the extracting solution under reduced pressure, carrying out column chromatography on the obtained product in a silica gel column, and concentrating the eluent under reduced pressure to obtain an esterified product intermediate of the intermediate ligand.
The preparation method of the 3, 5-ethyl phthalate phenylboronic acid comprises the following steps: 12.6g (0.06mol) of 3, 5-dicarboxyphenylboronic acid was added to a reaction flask, 300mL of absolute ethanol was added thereto, and after stirring the mixture uniformly, 12mL of concentrated sulfuric acid was added dropwise. After that, the mixture was heated to reflux and reacted under reflux for 12 hours. After the reaction is finished, ethanol is removed by decompression and concentration. The reaction product was carefully dropped into 500mL of an aqueous sodium bicarbonate solution (10mol/L), and a large amount of white floc was precipitated. The resulting white product was filtered, washed with water to neutral pH and dried at 60 ℃ for 12 hours. The obtained product is dissolved in 100mL of ethyl acetate and recrystallized to obtain the product of 3, 5-ethyl phthalate phenylboronic acid.
2) 5.0g of the esterified intermediate was put in a three-necked flask, 100ml of ethanol and 100ml of tetrahydrofuran were added thereto, and after dissolving by stirring, 150ml of an aqueous sodium hydroxide solution (4mol/L) was added thereto and dissolved by stirring. The reaction solution was heated to reflux and reacted under reflux for 12 hours, and the progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction, insoluble matter was removed by filtration, and the filtrate was transferred to a single-neck bottle and concentrated to remove the organic solvent. Then 100ml of distilled water is added for dilution, concentrated hydrochloric acid is dripped after the temperature is reduced to the room temperature, the pH value of the reaction solution is adjusted to about 3, and a large amount of white precipitate is separated out. The white precipitate was filtered, washed three times with distilled water, and dried at 60 ℃ for 12 hours to give a white-like powdery ligand, 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trimethoxybenzene.
Example 2
1) 1,3, 5-trihydroxy-2, 4, 6-tribromobenzene (CAS: 3354-82-3) (3.628g, 10mmol) and 3, 5-Dimethylate Phenylboronic acid (prepared as in example 1) (8.780, 33mmol) were charged to a reaction flask, and 21.0g of anhydrous potassium phosphate was added. The reactor was purged of oxygen using a vacuum line, followed by addition of tetrakis (triphenylphosphine) palladium (0.5g, 0.43mmol), addition of 300mL of deoxygenated dioxane, and reaction at 90 ℃ for 72 hours. Then filtering, decompressing and concentrating to remove the solvent, and extracting the reaction product by trichloromethane. And concentrating the extracting solution under reduced pressure, carrying out column chromatography on the obtained product in a silica gel column, and concentrating the eluent under reduced pressure to obtain an esterified product intermediate of the intermediate ligand.
2) 5.0g of the esterified intermediate was put in a three-necked flask, 100ml of ethanol and 100ml of tetrahydrofuran were added thereto, and after dissolving by stirring, 150ml of an aqueous sodium hydroxide solution (4mol/L) was added thereto and dissolved by stirring. The reaction solution was heated to reflux and reacted under reflux for 12 hours, and the progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction, insoluble matter was removed by filtration, and the filtrate was transferred to a single-neck bottle and concentrated to remove the organic solvent. Then 100ml of distilled water is added for dilution, concentrated hydrochloric acid is dripped after the temperature is reduced to the room temperature, the pH value of the reaction solution is adjusted to about 3, and a large amount of white precipitate is separated out. The white precipitate was filtered, washed three times with distilled water, and dried at 60 ℃ for 12 hours to give the off-white powdered ligand, 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trihydroxybenzene.
Example 3
0.066 g of 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trimethoxybenzene prepared in example 1 and 0.060 g of cadmium nitrate hexahydrate were charged into a polytetrafluoroethylene-lined reaction vessel, 8 ml of DMF and 4 ml of acetonitrile were added, 50. mu.l of concentrated nitric acid (mass concentration: 68 wt%) was added, dissolved by stirring, and sealed;
and (3) placing the reaction kettle in an oven to react for 72 hours at 100 ℃, then filtering (carrying out vacuum filtration under the vacuum degree of 1 KPa), washing with ethanol, and drying at 100 ℃ to obtain the organic amine cation modified metal-organic framework material.
Example 4
0.066 g of 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trimethoxybenzene prepared in example 1 and 0.060 g of zinc nitrate hexahydrate were charged in a polytetrafluoroethylene-lined reaction vessel, 8 ml of DMF and 4 ml of acetonitrile were added, 50. mu.l of concentrated nitric acid (mass concentration: 68 wt%) was added, dissolved by stirring, and sealed;
and (3) placing the reaction kettle in an oven to react for 72 hours at 100 ℃, then filtering (carrying out vacuum filtration under the vacuum degree of 1 KPa), washing with ethanol, and drying at 100 ℃ to obtain the organic amine cation modified metal-organic framework material.
Example 5
0.064 g of 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trihydroxybenzene prepared in example 2 and 0.060 g of cadmium nitrate hexahydrate are charged into a polytetrafluoroethylene-lined reaction vessel, 8 ml of DMF and 4 ml of acetonitrile are added, 50. mu.l of concentrated nitric acid (mass concentration: 68 wt%) is added, dissolved by stirring and sealed;
and (3) placing the reaction kettle in an oven to react for 72 hours at 100 ℃, then filtering (carrying out vacuum filtration under the vacuum degree of 1 KPa), washing with ethanol, and drying at 100 ℃ to obtain the organic amine cation modified metal-organic framework material.
Example 6
0.064 g of 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trihydroxybenzene prepared in example 2 and 0.060 g of zinc nitrate hexahydrate are charged into a polytetrafluoroethylene-lined reaction vessel, 8 ml of DMF and 4 ml of acetonitrile are added, 50. mu.l of concentrated nitric acid (mass concentration: 68 wt%) is added, dissolved by stirring and sealed;
and (3) placing the reaction kettle in an oven to react for 72 hours at 100 ℃, then filtering, (carrying out vacuum filtration under the vacuum degree of 1 KPa), washing with ethanol, and drying at 100 ℃ to obtain the organic amine cation modified metal-organic framework material.
Performance detection
The crystal structure stacking diagram of the organic amine cation modified metal-organic framework material prepared in the embodiment 3 of the invention is shown in figure 1.
The X-ray diffraction pattern of the organic amine cation modified metal-organic framework material prepared in example 3 of the present invention was tested, as shown in fig. 2; as can be seen from fig. 2, the powder diffraction Pattern (PXRD) of the metal-organic framework material prepared in example 3 is consistent with the PXRD pattern simulated by the single crystal data, which indicates that the structure of the metal-organic framework material is consistent with the single crystal structure and does not contain any impurity phase.
The metal-organic framework material modified by organic amine cations, which is prepared in embodiment 3 of the present invention, is subjected to X-ray single crystal diffraction detection, and a crystal data output image is obtained by analyzing the obtained single crystal diffraction data, as shown in fig. 3, it can be seen from fig. 3 that, under the influence of steric hindrance of the methoxy functional group, the spatial extension direction of the 3, 5-dicarboxyl group on the ligand rotates to a certain degree, and the angle between the benzene ring where the 3, 5-dicarboxyl group is located and the central benzene ring is 73.3 °; metallic ion Zn2+With 6 carboxyl groups of the ligandCoordination of 4 carboxyl groups with Zn2+Coordination is carried out by adopting a chelating coordination mode, and 2 carboxyl groups are coordinated with Zn2+Coordination is carried out by cis-cis bridging.
The X-ray diffraction pattern of the organic amine cation modified metal-organic framework material prepared in example 4 of the present invention was tested, as shown in fig. 4; as can be seen from fig. 4, the powder diffraction Pattern (PXRD) of the metal-organic framework material prepared in example 4 is consistent with the PXRD pattern simulated by the single crystal data, which indicates that the structure of the metal-organic framework material is consistent with the single crystal structure and does not contain any impurity phase.
The metal-organic framework material modified by organic amine cations, which is prepared in example 5 of the present invention, is subjected to X-ray single crystal diffraction detection, and a crystal data output image obtained by analyzing the obtained single crystal diffraction data is shown in fig. 5, it can be seen from fig. 5 that, under the influence of steric hindrance of the hydroxyl functional group, the spatial extension direction of the 3, 5-dicarboxyl group on the ligand rotates to a certain degree, and the angle between the benzene ring where the 3, 5-dicarboxyl group is located and the central benzene ring is 73.6 °; metallic ion Zn2+Coordinated to 6 carboxyl groups of the ligand, 4 of which are Zn2+Coordination is carried out by adopting a chelating coordination mode, and 2 carboxyl groups are coordinated with Zn2+Coordination is carried out by cis-cis bridging.
The nitrogen adsorption curve of the organic amine cation modified metal-organic framework material (cadmium is used as the metal center) obtained in example 3 of the present invention is shown in fig. 6, the test method of the nitrogen adsorption curve is performed according to gb.t19587-2004 method for determining the specific surface area of a solid substance according to the BET principle of gas adsorption, and the test equipment is a fully automatic specific surface area analyzer (Autosorb-iq) manufactured by kanta corporation; as can be seen from FIG. 6, the pore structure of the metal-organic framework material prepared in example 3 is microporous, and the specific surface area thereof is 975m2/g。
The nitrogen adsorption curve of the organic amine cation modified metal-organic framework material (with zinc as the metal center) prepared in example 4 of the invention is shown in fig. 7; following the test method described above; as can be seen from FIG. 7, the pore structure of the metal-organic framework material prepared in example 4 is microporous, and the specific surface area thereof is 983m2/g。
The carbon dioxide adsorption curve of the organic amine cation modified metal-organic framework material prepared in test example 3 at room temperature is shown in fig. 8; measuring the carbon dioxide adsorption curve by a volumetric method, wherein the testing instrument is a fully-automatic high-temperature high-pressure gas adsorption instrument (BSD-PH) produced by Bechard instruments science and technology Limited; as can be seen from fig. 8, the adsorption of carbon dioxide at room temperature by the metal-organic framework material prepared in example 3 shows an I-type adsorption isotherm, and the adsorption amount gradually increases with decreasing temperature, indicating that the metal-organic framework material has a strong adsorption capacity for carbon dioxide at room temperature.
The adsorption isotherm of the organic amine cation-modified metal-organic framework material prepared in test example 3 for hydrogen at room temperature (293K) is shown in fig. 9; the hydrogen adsorption curve is measured by a volumetric method, and the testing instrument is a full-automatic high-temperature high-pressure gas adsorption instrument (BSD-PH) produced by Bechard instruments science and technology Limited; as can be seen from FIG. 9, the hydrogen adsorption isotherm of the organic amine cation modified metal-organic framework material at room temperature (293K) is approximately a straight line, and the adsorption capacity at 20bar is smaller, namely 0.78mmol/g, which is closer to the hydrogen adsorption capacity of the conventional porous material.
The adsorbed amount of nitrogen was 1.25 mmol/g. At room temperature, the adsorption capacity of the metal-organic framework material to hydrogen and nitrogen is weak, the adsorption selectivity of carbon dioxide/nitrogen and carbon dioxide/hydrogen calculated according to an ideal solution adsorption theory is respectively 64 and 191 by combining the adsorption result to carbon dioxide, and the metal-organic framework material is positioned at the front position in the currently reported MOF material, so that the metal-organic framework material has obvious capacity of selectively adsorbing carbon dioxide.
The invention provides an organic amine cation modified metal-organic framework material, which takes the metal-organic framework material as a material for separating carbon dioxide, and has important significance for improving the adsorption separation property of the carbon dioxide and improving the carbon dioxide separation performance of the metal-organic framework material; the organic functional group on the organic ligand has important influence on the adjustment of the topological structure of the metal-organic framework material; the spatial configuration of the organic ligand in the metal-organic framework material can be changed by modifying functional groups on the organic ligand; these different spatial configurations are of great importance for obtaining metal-organic framework materials with specific configurations; according to the invention, organic amine cations can be generated in situ in the pore channel of the metal-organic framework material, so that the framework damage to the metal-organic framework material caused by a post-modification method is avoided, and meanwhile, the method also reduces the operation steps; the metal-organic framework material modified by the organic amine cations, which is prepared by the invention, has alkaline groups and unbalanced charges, so that the acting force between carbon dioxide molecules and the metal-organic framework material is greatly improved, the adsorption selectivity of the metal-organic framework material on carbon dioxide is obviously improved, and the carbon dioxide separation performance of the metal-organic framework material is improved.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing an organic amine cation modified metal-organic framework material comprises the following steps:
mixing an organic ligand and a metal ion compound in a solvent and a regulator to obtain a mixture;
and reacting the mixture to obtain the organic amine cation modified metal-organic framework material.
2. The method of claim 1, wherein the organic ligand is a carboxylic acid ligand comprising a functional group.
3. The method according to claim 2, wherein the number of carbon chains of the functional group is 1 to 3.
4. The method according to claim 3, wherein the organic ligand is selected from one or more of 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trimethoxybenzene, 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trihydroxybenzene and 1,3, 5-tris (3, 5-dicarboxyphenyl) -2,4, 6-trimethylbenzene.
5. The method of claim 1, wherein the metal ionic compound is a transition metal ionic compound.
6. The method of claim 1, wherein the molar ratio of organic ligand to metal ion compound is 1: (0.5-2).
7. The method according to claim 1, wherein the solvent is one or more selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, and N, N-diethylformamide.
8. The method of claim 1, wherein the modulating agent is an acid.
9. The method according to claim 1, wherein the reaction temperature is 60 to 150 ℃.
10. An organic amine cation modified metal-organic framework material prepared by the method of claim 1.
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| CN101816924A (en) * | 2010-04-13 | 2010-09-01 | 东南大学 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
| US20110104213A1 (en) * | 2009-10-30 | 2011-05-05 | University Of Pittsburgh-Of The Commonwealth System Of Higher Education | Porous Biomolecule-Containing Metal-Organic Frameworks |
| US20150299226A1 (en) * | 2014-04-16 | 2015-10-22 | New Mexico Highlands University | Tunable metal-organic frameworks |
| CN109517184A (en) * | 2017-09-19 | 2019-03-26 | 南开大学 | A kind of metal-organic framework material, preparation method and application |
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| US20110104213A1 (en) * | 2009-10-30 | 2011-05-05 | University Of Pittsburgh-Of The Commonwealth System Of Higher Education | Porous Biomolecule-Containing Metal-Organic Frameworks |
| CN101816924A (en) * | 2010-04-13 | 2010-09-01 | 东南大学 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
| US20150299226A1 (en) * | 2014-04-16 | 2015-10-22 | New Mexico Highlands University | Tunable metal-organic frameworks |
| CN109517184A (en) * | 2017-09-19 | 2019-03-26 | 南开大学 | A kind of metal-organic framework material, preparation method and application |
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