CN109851810B - Borane anion supramolecular organic framework material and preparation method and application thereof - Google Patents
Borane anion supramolecular organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a borane anion supermolecule organic framework material, which is characterized in that metal ions M and organic nitrogen-containing ligands L are coordinated to form a two-dimensional plane structure, and cage-shaped borane anions [ B ] are used12H12]2‑Or [ B10H10]2‑The organic nitrogen-containing ligand L is obtained by connecting various negative hydrogen-positive hydrogen dihydro bond actions, negative hydrogen-metal actions and other supermolecule actions to form a three-dimensional framework structure, wherein metal ions M are selected from at least one of Zn, Cu, Ni and Co, and the organic nitrogen-containing ligand L is selected from at least one of pyrazine, bipyridine acetylene, bipyridine ethylene, bipyridine benzene and azo bipyridine. The borane anion supramolecular organic framework material can be used for high-selectivity adsorption and separation of propane/ethane/methane, carbon dioxide/methane and acetylene/ethylene.
Description
Technical Field
The invention relates to the field of synthesis of porous materials and gas adsorption, in particular to a borane anion supramolecular organic framework material and a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) are emerging porous crystalline materials, which have attracted extensive attention due to the designability of their channels, pore diameters and pore surface environments, and exhibit great application potential in the field of gas storage and separation.
The existing metal organic framework is mainly assembled by coordination of metal and organic ligand; whereas hydrogen-bonded organic framework materials are assembled mainly by hydrogen bonding. The variable metal center and organic ligand of the metal-organic framework material lead to the diversity of the structure and function. The selection of the metal center covers almost all metals, among which the transition metals Zn, Cu, Fe, etc. are used more often. Different materials may also be present due to differences in the valence state of the metal, differences in the coordination capacity. For the selection of organic ligands, nitrogen-containing heterocyclic ligands to carboxylic ligands are widely used.
The hydrogen bond organic framework material is only constructed by orderly self-assembling organic units through intermolecular hydrogen bonds, and has the unique advantages of mild synthesis conditions and easy regeneration. However, the low stability of hydrogen-bonded organic framework materials has severely hampered their development and also limited the range of potential applications for such materials.
Porous materials assembled by atypical supramolecular interactions such as negative hydrogen-positive hydrogen dihydro bond interactions and negative hydrogen-metal interactions have not been reported. The material is expected to combine the advantages of metal organic framework materials and hydrogen bond organic framework materials, and has unique performance and advantages in the field of gas separation.
However, the number of the structural units containing negative hydrogen is not very large, and some of the structural units have strong reducibility and are unstable, such as sodium borohydride, and cannot be used for material synthesis. And the cage-shaped polyhedral boron hydride anion shows stronger thermal stability and chemical stability due to the delocalization of the charge, and is expected to be applied to the synthesis of porous materials.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a borane anion supramolecular organic framework material which is prepared by firstly forming a two-dimensional plane structure by coordination of metal ions M and organic nitrogen-containing ligands L and then passing cage-shaped borane anions [ B ]12H12]2-Or [ B10H10]2--The three-dimensional framework structure is formed by the connection of various negative hydrogen-positive hydrogen dihydro bond actions, negative hydrogen-metal actions and other supermolecule actions, and can be used for high-selectivity adsorption and separation of propane/ethane/methane, carbon dioxide/methane and acetylene/ethylene.
A supermolecule organic frame material of borane anion is prepared through coordinating metal ion M with organic nitrogen-containing ligand L to form two-dimensional planar structure, and coordinating with cage-shaped borane anion [ B ]12H12]2-Or [ B10H10]2-Connecting to form a three-dimensional frame structure;
the caged borane anion [ B12H12]2-The structural formula of (A) is shown as formula (I):
the caged borane anion [ B10H10]2-The structural formula of (II):
preferably, the metal ion M is at least one selected from Zn, Cu, Ni and Co.
Preferably, the organic nitrogen-containing ligand L is at least one selected from pyrazine, bipyridine acetylene, bipyridine ethylene, bipyridine benzene and azo bipyridine, and the corresponding chemical structural formulas are respectively as follows:
the invention also provides a preparation method of the borane anion supramolecular organic framework material, which comprises the following steps:
(1) dissolving a salt containing metal ions M and a borane anion salt in water, dissolving an organic nitrogen-containing ligand L in a solvent A, mixing the two solutions, stirring for 24-48 h at 25-100 ℃, and filtering to obtain a solid precipitate product; the solvent A is at least one of methanol, ethanol, acetone and acetonitrile;
(2) and (3) placing the solid precipitation product in a solvent A for exchange to remove water molecules, wherein the exchange time is 5-7 h each time, and then vacuumizing and degassing at 60-100 ℃ for activation for 12-24 h to obtain the borane anion supramolecular organic framework material.
Preferably, the salt of the metal ion M is nitrate and/or tetrafluoroborate. The nitrate and/or tetrafluoroborate of the metal ion M has good solubility in aqueous solution and organic polar solvent, and the nitrate and tetrafluoroborate are easy to dissociate, which is beneficial to the reaction.
Preferably, the borane anion salt is a sodium salt or an ammonium salt of a borane anion. The borane anion sodium salt or ammonium salt has better solubility in a polar solvent, and is beneficial to the reaction.
The metal ion M is divalent and the borane anion is divalent, and the ratio of the metal ion M to the borane anion is 1:1 in order to realize charge balance. The metal ion M is typically hexacoordinated, requiring 4 nitrogens in the 4 other positions in addition to the two borane B-H coordinates, and the ratio of metal ion M to nitrogen-containing organic ligand is 1:2 since the organic nitrogen-containing ligand L is two nitrogens. Therefore, the molar ratio of the salt of the metal ion M, the salt of the borane anion and the organic nitrogen-containing ligand L is preferably 1:1: 2.
When the molar ratio of the salt of the metal ion M, the borane anion salt and the organic nitrogen-containing ligand L is not 1:1:2, the reaction also proceeds, but the yield is reduced and impurities are increased.
Preferably, the solid precipitated product is placed in solvent A for more than 3 repeated exchanges, with the removal of water molecules as far as possible. This operation facilitates degassing activation of the borane anionic supramolecular organic framework material.
The invention also provides application of the borane anion supramolecular organic framework material in the field of selective adsorption and separation of gases.
The borane anion supramolecular organic framework material can be used for selective adsorption separation of any two or three gases of propane/ethane/methane.
The borane anion supramolecular organic framework material can also be used for selective adsorption separation of carbon dioxide/methane.
The borane anion supramolecular organic framework material can also be used for selective adsorption separation of acetylene/ethylene.
The application principle of the borane anion supramolecular organic framework material in the field of selective adsorption and separation of gases is based on that the borane anion supramolecular organic framework material has an action site with a proper pore size and high density, the size of the action site can be finely regulated and controlled, the action site can selectively react with different gas molecules, and efficient selective adsorption and separation of gases are realized.
Compared with the prior art, the invention has the main advantages that:
(1) the borane anion supramolecular organic framework material designed and synthesized by the invention has unique structural characteristics, and borane anions, metal cations and nitrogen-containing organic ligands are linked through multiple supramolecular actions, so that the structure has better stability and is beneficial to practical application.
(2) The borane anion inorganic ligand adopted by the invention is different from traditional anions such as nitric acid, sulfuric acid, hexafluorosilicic acid and the like, is used for synthesizing a porous metal framework material for the first time, has a 3D cage-shaped structure, and has abundant binding sites which are beneficial to acting with gas molecules to realize selective separation.
(3) The borane anion supramolecular organic framework material designed and synthesized by the invention has extremely high separation selectivity on propane/ethane/methane, and is superior to most reported metal framework materials, carbon materials and molecular sieve materials containing saturated metal sites.
(4) The borane anion supermolecule organic framework material designed and synthesized by the invention has high separation selectivity on carbon dioxide/methane
(5) The borane anion supermolecule organic framework material designed and synthesized by the invention has high separation selectivity on acetylene/ethylene.
Drawings
FIG. 1 is a caged borane anion [ B ]12H12]2-Or [ B10H10]2-Schematic structural diagram of (a);
FIG. 2 is a schematic crystal structure of BSF-1 of the borane anion supramolecular organic framework material in example 1;
FIG. 3 is a graph showing the 77K nitrogen adsorption and desorption of BSF-1 in example 1;
FIG. 4 is a graph showing isothermal adsorption and desorption curves of acetylene in BSF-1 at 273K, 298K and 313K in example 1;
FIG. 5 is a graph showing the isothermal adsorption and desorption curves of ethylene at 273K, 298K and 313K in BSF-1 in example 1;
FIG. 6 is a graph showing the isothermal adsorption and desorption of carbon dioxide in BSF-1 at 273K, 298K and 313K in example 1;
FIG. 7 is a graph showing isothermal adsorption and desorption curves of propane at 273K, 298K and 313K in BSF-1 in example 1;
FIG. 8 is a graph of isothermal adsorption and desorption of ethane at BSF-1 at 273K, 298K, 313K in example 1;
FIG. 9 is a graph showing isothermal adsorption and desorption curves of methane at BSF-1 at 273K, 298K and 313K in example 1;
FIG. 10 is a calculated thermal map of propane, ethane, acetylene, ethylene, carbon dioxide adsorption of BSF-1 from isotherms obtained in example 1;
FIG. 11 is a graph of IAST selectivity on BSF-1 for the mixed gases propane/methane, ethane/methane, carbon dioxide/methane, acetylene/ethylene, acetylene/carbon dioxide, and acetylene/ethylene calculated from isotherms in example 1;
FIGS. 12a and 12b are graphs showing the breakthrough of the mixed gas of propane/methane and ethane/methane in BSF-1 in example 1, respectively;
FIG. 12c is a graph of the cyclic carbon dioxide adsorption-desorption curves for BSF-1 of example 1;
FIG. 12d is the X-ray diffraction (XRD) pattern of BSF-1 from example 1.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Caged borane anions [ B ] for use in the present invention12H12]2-Or [ B10H10]2-The structure of (2) is shown in fig. 1.
Example 1
In a 50mL round-bottomed flask, 242mg (1mmol) of Cu (NO)3)·3H2O and 212mg (1mmol) of Na2B12H12Dissolved in 10 ml of water. In a further 25mL round-bottom flask, 360mg (2mmol) of 4, 4' -bipyridinylacetylene were dissolved in 15 mL of methanol. Slowly adding methanol solution into the water solution, stirring at 25 deg.C for 24 hr to obtain purple solid precipitate, filtering, and washing with methanol. And (3) replacing the solid in anhydrous methanol for 3 times at intervals of 6h, removing water molecules in pores of the material, and then vacuumizing and degassing at 100 ℃ for activation for 12h to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-1 (bonded-submicron organic framework).
FIG. 2 is a schematic of the crystal structure of BSF-1, in which copper is coordinated to four different pyridine rings in the horizontal direction and then infinitely extended to form a planar structure, and copper is coordinated to the B-H of two different boranes in the vertical direction. Each borane connects two different copper chains, linking up a planar structure consisting of Cu and bipyridylacetylene in the vertical direction, forming a three-dimensional layered columnar structure.
Subjecting the activated material to 77K N under liquid nitrogen condition2The results of the adsorption-desorption experiments are shown in fig. 3, so that parameters such as the specific surface area, the pore volume and the like of the BSF-1 are obtained. 77K N2The adsorption experiment shows that the BET specific surface area of BSF-1 is 535cm2Per g, pore volume 0.25cm3G, and 0.27cm calculated from single crystal data3The/g is more consistent. Then measuring single-component adsorption curves of propane, ethane, methane, acetylene, ethylene and carbon dioxide of BSF-1 at 273K, 298K and 313K by using Clausians-ClapThe heat of adsorption curve of BSF-1 to the above gases is calculated and fitted by the Eyron equation, as shown in FIGS. 4-9. The tendency of the adsorption energy was propane (48kJ/mol)>Ethane (32kJ/mol)>Methane (23kJ/mmol), acetylene (36kJ/mol)>Ethylene (25kJ/mmol)>Carbon dioxide (22kJ/mol) was found to have the same gradient as that of the adsorption curves shown in FIGS. 4 to 9. FIG. 10 is a calculated thermal map of the adsorption of propane, ethane, acetylene, ethylene, carbon dioxide for BSF-1 based on isotherms. As shown in fig. 11, the separation selectivity for propane/methane, ethane/methane, carbon dioxide/methane, acetylene/ethylene for single component gas and two component gas was found based on ideal adsorption solution theory (iatt) and fitting of adsorption data, wherein the propane/methane selectivity was up to 353, ethane/methane up to 23, and carbon dioxide/methane, acetylene/ethylene selectivity was 7.5 and 2.3.
Grinding 0.5g of BSF-1 into fine powder, filling the powder into an adsorption column with the inner diameter of 4.6mm and the length of 100mm, and respectively introducing propane/methane mixed gas and ethane/methane mixed gas into the adsorption column at 1mL/min at the room temperature of 25 ℃, wherein methane is quickly discharged, and propane and ethane are respectively reserved in the adsorption column for 86min/g and 60min/g as shown in figures 12a and 12 b; as shown in fig. 12c, when BSF-1 is subjected to cyclic carbon dioxide adsorption-desorption, the adsorption curve is unchanged, indicating that the cyclic performance is good; as shown in fig. 12d, BSF-1 was soaked in water for 1 month with no change in XRD pattern, indicating that the water stability of the borane anion hybrid material was good.
Example 2
In a 50mL round bottom flask, 291mg (1mmol) of Co (NO) was added3)·6H2O and 212mg (1mmol) of Na2B12H12Dissolved in 10 ml of water. In a further 25mL round-bottom flask, 312mg (2mmol) of 4, 4' -bipyridine were dissolved in 15 mL of acetone. Slowly adding acetone solution into the water solution, stirring at 50 deg.C for 48 hr to obtain yellow solid precipitate, filtering, and washing with acetone. And (3) replacing the solid in anhydrous acetone for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping, degassing and activating for 24h at 60 ℃ to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-2.
And (3) measuring single-component adsorption curves of propane, ethane and methane of the activated BSF-2 at 298K, and calculating and fitting an isothermal adsorption curve of the BSF-2 to the gases by using a Clausians-Clapeyron equation. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the two-component gas propane/methane and ethane/methane is as high as 305 and 32.
Grinding 0.5g BSF-2 into fine powder, loading into an adsorption column with an inner diameter of 4.6mm and a length of 50mm, introducing a mixed gas of propane/methane and ethane/methane into the adsorption column at room temperature of 25 ℃ at a rate of 2mL/min, wherein methane comes out quickly, and propane and ethane are retained in the adsorption column for 65min/g and 33 min/g.
Example 3
In a 50mL round bottom flask, 291mg (1mmol) of Co (NO) was added3)·6H2O and 174mg (1mmol) of Na2B10H10Dissolved in 10 ml of water. In a further 25mL round-bottom flask, 312mg (2mmol) of 4, 4' -bipyridine were dissolved in 15 mL of acetone. Slowly adding the acetone solution into the water solution, stirring at 80 deg.C for 24 hr to obtain yellow solid precipitate, filtering, and washing with acetone. And (3) replacing the solid in anhydrous acetone for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping, degassing and activation at 60 ℃ for 12h to obtain the borane anion supramolecular organic framework material, which is named as BSF-3.
And (3) measuring single-component adsorption curves of carbon dioxide and methane of the activated BSF-3 at 298K, and calculating and fitting an isothermal adsorption curve of the BSF-3 to the gases by using a Clausians-Clapeyron equation. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the bi-component gas carbon dioxide/methane is up to 35.
Example 4
In a 50mL round bottom flask, 297mg (1mmol) of Zn (NO) was added3)2·6H2O and 174mg (1mmol) of Na2B10H10Dissolved in 10 ml of water. In a further 25mL round-bottom flask 368mg (2mmol) of 4, 4' -azobispyridine are dissolved in 15 mL of acetone. Mixing the powderThe ketone solution was slowly added to the aqueous solution and stirred at 100 ℃ for 24h to give a white solid precipitate, which was filtered and washed with acetone. And (3) replacing the solid in anhydrous acetone for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping degassing activation at 60 ℃ for 12h to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-4.
Example 5
In a 50mL round-bottom flask, 340mg (1mmol) of Ni (BF) was charged2·6H2O and 174mg (1mmol) of Na2B10H10Dissolved in 10 ml of water. In a further 25mL round-bottom flask 368mg (2mmol) of 4, 4' -azobispyridine are dissolved in 10 mL of ethanol. Slowly adding ethanol solution into the water solution, stirring at 25 deg.C for 24 hr to obtain green solid precipitate, filtering, and washing with ethanol. And (3) replacing the solid in absolute ethyl alcohol for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping, degassing and activating for 12h at 60 ℃ to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-5.
Example 6
In a 50mL round-bottom flask, a solution containing 237mg (1mmol) of Cu (BF)2And 174mg (1mmol) of Na2B10H10Dissolved in 10 ml of water. In a further 25mL round-bottom flask, 464mg (2mmol) of bipyridine benzene was dissolved in 20 mL of ethanol. Slowly adding the acetonitrile solution into the water solution, stirring for 48h at 100 ℃ to obtain a purple solid precipitate, filtering, and washing with acetonitrile. And (3) replacing the solid in anhydrous acetonitrile for 3 times, wherein the interval between every two times is 6h, removing water molecules in pores of the material, and then vacuumizing and degassing at 60 ℃ for activation for 12h to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-6.
Example 7
In a 50mL round bottom flask, 297mg (1mmol) of Zn (NO) was added3)2·6H2O and 212mg (1mmol) of Na2B12H12Dissolved in 10 ml of water. In another 25mL round-bottom flaskIn (2mmol), 464mg (2mmol) of bipyridine benzene was dissolved in 20 ml of ethanol. Slowly adding acetonitrile solution into the water solution, stirring for 40h at 80 ℃ to obtain white solid precipitate, filtering, and washing with acetonitrile. And (3) replacing the solid in anhydrous acetonitrile for 3 times, wherein the interval between every two times is 6h, removing water molecules in pores of the material, and then vacuumizing and degassing at 60 ℃ for activation for 24h to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-7.
And (3) measuring single-component adsorption curves of carbon dioxide and methane of the activated BSF-7 at 298K, and calculating and fitting an isothermal adsorption curve of the BSF-7 to the gases by using a Clausians-Clapeyron equation. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the bi-component gas carbon dioxide/methane is up to 35.
Example 8
In a 50mL round-bottom flask, a solution containing 237mg (1mmol) of Cu (BF)2And 212mg (1mmol) of Na2B12H12Dissolved in 10 ml of water. In a further 25mL round-bottom flask, 464mg (2mmol) of bipyridine benzene was dissolved in 20 mL of ethanol. Slowly adding ethanol solution into the water solution, stirring at 100 deg.C for 48 hr to obtain blue solid precipitate, filtering, and washing with ethanol. And (3) replacing the solid in absolute ethyl alcohol for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping, degassing and activating for 12h at 100 ℃ to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-8.
And (3) measuring the single-component adsorption curve of acetylene and ethylene in the activated BSF-8 at 298K, and calculating and fitting the adsorption heat curve of the BSF-8 to the gases by using a Clausians-Clapeyron equation. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the bi-component gas acetylene/ethylene is up to 18.
Example 9
In a 50mL round-bottomed flask, 242mg (1mmol) of Cu (NO)3)·3H2O and 212mg (1mmol) of Na2B12H12Dissolved in 10 ml of water. In another 25mL round bottomIn a flask, 364mg (2mmol) of bipyridyl ethylene was dissolved in 15 ml of methanol. Slowly adding methanol solution into the water solution, stirring at 50 deg.C for 48 hr to obtain blue solid precipitate, filtering, and washing with methanol. And (3) replacing the solid in anhydrous methanol for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping degassing activation at 100 ℃ for 12h to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-9.
And (3) measuring the single-component adsorption curve of acetylene and ethylene in the activated BSF-9 at 298K, and calculating and fitting the isothermal adsorption curve of the BSF-9 to the gases by using a Clausians-Clapeyron equation. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the bi-component gas acetylene/ethylene is up to 20.
Example 10
In a 50mL round-bottomed flask, 242mg (1mmol) of Cu (NO)3)·3H2O and 164mg (1mmol) of (NH)4)2B10H10Dissolved in 10 ml of water. In a further 25mL round-bottom flask, 364mg (2mmol) of bipyridyl ethylene was dissolved in 15 mL of methanol. Slowly adding methanol solution into the water solution, stirring at 50 deg.C for 48 hr to obtain blue solid precipitate, filtering, and washing with methanol. And (3) replacing the solid in anhydrous methanol for 3 times at intervals of 6h, removing water molecules in pores of the material, and performing vacuum-pumping degassing activation at 100 ℃ for 12h to obtain the borane anion supramolecular organic framework material for gas separation, which is named as BSF-10.
And (3) measuring single-component adsorption curves of carbon dioxide and methane of the activated BSF-10 at 298K, and calculating and fitting an adsorption curve of BSF-7 to the gases by using a Clausians-Clapeyron equation. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the bi-component gas carbon dioxide/methane is as high as 52.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (9)
1. A borane anion supermolecule organic framework material is characterized in that a metal ion M is coordinated with an organic nitrogen-containing ligand L to form a two-dimensional plane structure, and then the two-dimensional plane structure is coordinated with a caged borane anion [ B ]12H12]2-Or [ B10H10]2-Connecting to form a three-dimensional frame structure; the metal ion M is at least one selected from Zn, Cu, Ni and Co; the organic nitrogen-containing ligand L is at least one selected from pyrazine, bipyridine acetylene, bipyridine ethylene, bipyridine benzene and azo bipyridine;
the caged borane anion [ B12H12]2-The structural formula of (A) is shown as formula (I):
the caged borane anion [ B10H10]2-The structural formula of (II):
2. a method for the preparation of borane anionic supramolecular organic framework materials according to claim 1, comprising:
(1) dissolving a salt containing metal ions M and a borane anion salt in water, dissolving an organic nitrogen-containing ligand L in a solvent A, mixing the two solutions, stirring for 24-48 h at 25-100 ℃, and filtering to obtain a solid precipitate product; the solvent A is at least one of methanol, ethanol, acetone and acetonitrile;
(2) and (3) placing the solid precipitation product in a solvent A for exchange to remove water molecules, wherein the exchange time is 5-7 h each time, and then vacuumizing and degassing at 60-100 ℃ for activation for 12-24 h to obtain the borane anion supramolecular organic framework material.
3. Process for the preparation of borane anionic supramolecular organic framework materials according to claim 2, characterized in that the salts of metal ions M are nitrates and/or tetrafluoroborates.
4. A method for the preparation of borane anion supramolecular organic framework material as claimed in claim 2, characterized in that the borane anion salt is sodium or ammonium salt of borane anion.
5. The method for preparing the borane anion supramolecular organic framework material as claimed in claim 2, wherein the molar ratio of the salt of the metal ion M, the salt of the borane anion and the organic nitrogen-containing ligand L is 1:1: 2.
6. Use of borane anion supramolecular organic framework material according to claim 1 in the field of selective adsorption separation of gases.
7. Use of borane anion supramolecular organic framework material in the field of selective adsorption separation of gases according to claim 6, characterized in that the borane anion supramolecular organic framework material is used for selective adsorption separation of any two or three gases of propane/ethane/methane.
8. Use of borane anion supramolecular organic framework material in the field of selective adsorption separation of gases according to claim 6, characterized in that the borane anion supramolecular organic framework material is used for selective adsorption separation of carbon dioxide/methane.
9. The use of borane anion supramolecular organic framework material in the field of selective adsorption separation of gases according to claim 6, characterized in that the borane anion supramolecular organic framework material is used for selective adsorption separation of acetylene/ethylene.
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| US7824473B2 (en) * | 2007-07-27 | 2010-11-02 | Northwestern University | Metal-organic framework materials based on icosahedral boranes and carboranes |
| CN103508434A (en) * | 2012-06-28 | 2014-01-15 | 中国科学院大连化学物理研究所 | Preparation method of boron/nitrogen-doped microporous carbon material |
| CN105713017A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | High selectivity metal organic skeleton material and preparation method thereof |
| CN105541886A (en) * | 2015-09-08 | 2016-05-04 | 哈尔滨工业大学无锡新材料研究院 | Carborane-containing metal-organic framework and preparation method thereof |
| CN105944680B (en) * | 2016-05-17 | 2018-12-25 | 浙江大学 | A kind of method of adsorbing separation propylene propine |
| CN107774234B (en) * | 2016-08-29 | 2020-03-17 | 中国石油化工股份有限公司 | Metal organic framework material and preparation method and application thereof |
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