CN114177890A - Hydrothermally stable column cage type metal organic framework material and preparation method and application thereof - Google Patents
Hydrothermally stable column cage type metal organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hydrothermally stable column cage type metal organic framework material, a preparation method thereof and application thereof in the field of selective adsorption and separation of gases. The column cage type metal-organic framework material is formed by self-assembly of metal ions M, nonlinear multidentate nitrogen-containing ligands L and high-coordination-number inorganic anions through coordination bonds. The column cage type metal organic framework material has good hydrothermal stability and good cyclicity, and can be used for high-selectivity adsorption separation of alkyne olefins such as acetylene/ethylene, propyne/propylene and the like.
Description
Technical Field
The invention relates to the field of synthesis of porous materials and gas adsorption, in particular to a hydrothermally stable column cage type metal organic framework material and a preparation method and application thereof.
Background
Metal-organic frameworks (MOFs) are a class of porous framework materials formed by assembling metal ions or clusters and organic ligands through coordination bonds.
The metal organic framework material is the most potential choice in the field of gas storage and separation due to the hole structure and the adjustability of the hole surface environment.
The anion pillared ordered porous material is a metal organic framework assembled by inorganic anions, metal ions and organic nitrogen-containing ligands through coordination.
The anion pillared ordered porous material usually adopts a linear type bidentate nitrogen-containing ligand, and the classical structure is as follows: the metal is firstly coordinated with four ligands in the horizontal direction, and a plane structure is formed after infinite extension; then coordinate with two pillared anions in the vertical direction to form a three-dimensional layer columnar structure.
Patent specification CN 110193352A discloses a functionalized caged borane anion pillared supramolecular microporous framework material made of metal Cu2+The ions are coordinated with a bidentate linear organic nitrogen-containing ligand L to form a two-dimensional plane structure, and then are substituted by iodine to form a functionalized cage-shaped dodecaborane anion [ B12H11I]2-The bridges form a three-dimensional layered cylindrical frame structure.
The patent specification with publication number CN 109851810A discloses a borane anion supramolecular organic framework material, which is characterized in that firstly, a metal ion M and a bidentate linear organic nitrogen-containing ligand L are coordinated to form a two-dimensional plane structure, and then, a cage-shaped borane anion [ B ] is used for preparing the material12H12]2-Or [ B10H10]2-The three-dimensional framework structure is obtained by connecting various negative hydrogen-positive hydrogen dihydro bond actions, negative hydrogen-metal actions and other supermolecule actions to form the three-dimensional framework structure.
The pillared anions such as polyfluoro anions can form strong hydrogen bond interaction with alkyne, so that the structure can obtain high selectivity of alkyne-alkene separation, but the adsorption capacity is not high, and efficient separation and purification cannot be realized.
Current research has shown that interconnected cage-shaped cavities have a larger storage volume than cylindrical one-dimensional channels.
By adopting tridentate nitrogen-containing organic matters or tetradentate nitrogen-containing organic matters as organic ligands to construct the anion pillared metal organic framework with cage-shaped pore cavities, the metal organic framework material with high selectivity and high adsorption capacity is expected to be obtained.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a hydrothermally stable cylindrical cage type metal organic framework material, which is characterized in that a metal ion M and a specific tridentate or tetradentate organic nitrogen-containing ligand L are coordinated to form a cage structure, and then pillared polyfluoro anions or borane anions are connected through coordination to form a cylindrical cage type three-dimensional framework structure, so that the cylindrical cage type metal organic framework material can be used for high-capacity and high-selectivity adsorption separation of propyne/propylene and acetylene/ethylene, and has excellent water stability and thermal stability.
The structure of the cylindrical cage type metal organic framework material formed by adopting the specific tridentate or tetradentate organic nitrogen-containing ligand L and the adsorption and separation mechanism of the cylindrical cage type metal organic framework material on gas are greatly different from the traditional anion pillared ordered porous material formed by the bidentate linear organic nitrogen-containing ligand.
Specifically, the method comprises the following steps:
a hydrothermally stable cylindrical cage type metal-organic framework material is formed by self-assembly of metal ions M, nonlinear multidentate nitrogen-containing ligands L and high-coordination-number inorganic anions through coordination bonds;
the metal ion M is Cu2+、Ni2+、Fe2+、Co2+、Zn2+At least one of;
the nonlinear multidentate nitrogen-containing ligand L has a structure represented by any one of the following formulas L1 to L7:
the inorganic anion with high coordination number is SiF6 2-、TiF6 2-、GeF6 2-、NbOF5 2-Or a boron cage anion;
the boron cage anion has a structure represented by the following formula (I) or (II):
in the nonlinear multidentate nitrogen-containing ligand L, L1-L6 is a tridentate ligand, and L7 is a tetradentate ligand.
Among the above-mentioned inorganic anions having a high coordination number, the polyfluoro anion SiF6 2-、TiF6 2-、GeF6 2-、NbOF5 2-The structures of (a) and (b) are respectively as follows:
the corresponding boron cage anion of formula (I) has the chemical formula [ B12H12]2-。
The corresponding boron cage anion of formula (II) has the chemical formula [ B10H10]2-。
The invention also provides a preferable preparation method of the hydrothermally stable column cage type metal organic framework material, which comprises the following steps:
(1) dissolving a salt containing metal ions M and a high-coordination-number inorganic anion salt in deionized water to obtain a solution X, dissolving a nonlinear multidentate nitrogen-containing ligand L in an organic solvent A to obtain a solution Y, dropwise adding the solution X into the solution Y, stirring for 24-72 h at 25-100 ℃, carrying out solid-liquid separation, and washing the obtained solid with the deionized water and the organic solvent A to obtain an intermediate product;
the organic solvent A is at least one of methanol, ethanol, acetone and acetonitrile;
(2) and soaking the intermediate product in an organic solvent A to displace and remove water molecules in the pore channels, wherein the displacement time is 5-12 h each time, displacing for 3-6 times, and then vacuumizing, degassing and activating for 10-24 h at 75-120 ℃ to obtain the hydrothermally stable column cage type metal organic framework material.
In a preferred example, in the step (1), the salt containing the metal ion M is a nitrate and/or a tetrafluoroborate of the metal ion M. The nitrate and/or tetrafluoroborate of the metal ion M have good solubility in the aqueous solution and the organic solvent A, and the nitrate and the tetrafluoroborate are easy to dissociate, which is beneficial to the reaction.
In a preferred embodiment, in step (1), the high coordination number inorganic anion salt is a sodium salt and/or an ammonium salt of the high coordination number inorganic anion. The sodium salt and/or ammonium salt of the inorganic anion with high coordination number has better solubility in the organic solvent A, thus being beneficial to the reaction.
The metal ion M is positive divalent, the inorganic anion with high coordination number is negative divalent, and the ratio of the metal ion M to the inorganic anion with high coordination number needs to be 1:1 in order to realize charge balance. The metal ion M is typically hexa-coordinated, four other positions require four nitrogens for coordination in addition to two high coordination number inorganic anions, and since the non-linear multidentate nitrogen-containing ligands L are all three or four nitrogens, the ratio of metal ion M to non-linear multidentate nitrogen-containing ligand L is 3:3:4 (tridentate ligand) or 1:1:1 (tetradentate ligand). Therefore, in step (1), the salt containing the metal ion M, the salt of the high-coordination-number inorganic anion, and the nonlinear multidentate nitrogen-containing ligand L are preferably added in a molar ratio of the metal ion M, the high-coordination-number inorganic anion, and the nonlinear multidentate nitrogen-containing ligand L of 3:3:4 or 1:1: 1.
When the salt containing the metal ion M, the salt of the high-coordination-number inorganic anion, and the nonlinear multidentate nitrogen-containing ligand L are not added in the above-mentioned proportions, the reaction proceeds, but the yield decreases and impurities increase.
Preferably, the intermediate product is exchanged repeatedly in the organic solvent a 3 to 6 times or more, removing water molecules as much as possible. This operation facilitates degassing activation of the column cage metal organic framework material.
The invention also provides application of the hydrothermally stable column cage type metal organic framework material in the field of selective adsorption and separation of gases.
The application principle of the hydrothermally stable column cage type metal organic framework material in the field of selective adsorption separation of gas is based on that the column cage type metal organic framework material has action sites with suitable pore diameter and high density, the size of the action sites can be finely regulated and controlled, the action sites can selectively react with different gas molecules, and meanwhile, a cage type structure provides a higher storage volume, so that high-capacity and high-selectivity adsorption separation of gas is realized.
In a preferred example, the hydrothermally stable cylindrical cage type metal organic framework material can be used for selective adsorption separation of acetylene/ethylene.
In another preferred example, the hydrothermally stable column cage type metal organic framework material can be used for selective adsorption separation of propyne/propylene.
Compared with the prior art, the invention has the main advantages that:
1. the column cage type metal organic framework material designed and synthesized by the invention has good hydrothermal stability and good cyclicity.
2. The organic ligand adopted by the invention is different from the traditional bidentate nitrogen-containing ligand, the formed framework material has a unique column cage type structure, and rich binding sites and the cage type structure can realize high-capacity and high-selectivity separation of gas.
3. The column cage type metal organic framework material designed and synthesized by the invention has ultrahigh adsorption capacity to propyne and acetylene no matter under low pressure or normal pressure, is superior to most reported column support anion materials, can realize trace alkyne adsorption in alkyne-olefin mixed gas, and realizes selective separation.
4. The column cage type metal organic framework material designed and synthesized by the invention can realize the high-efficiency separation of acetylene/ethylene.
5. The column cage type metal organic framework material designed and synthesized by the invention can realize the high-efficiency separation of propyne/propylene.
Drawings
FIG. 1 is a schematic diagram of the structure of a boron cage anion, a polyfluoro anion;
FIG. 2 is a schematic view showing a cylindrical cage type metal organic framework material (CuTiF) in example 16)3(L1)4A schematic of the crystal structure of (a);
FIG. 3 shows (CuTiF) in example 16)3(L1)477K nitrogen adsorption and desorption curve diagram;
FIG. 4 includes (CuTiF) in example 16)3(L1)4Thermogram of acetylene cycle adsorption-desorption, propyne/propylene penetration test result graph and X-ray diffraction (XRD) graph;
FIG. 5 shows the reaction of 278K, 298K, 308K acetylene in (CuSiF) in example 26)3(L1)4The isothermal adsorption-desorption curve diagram above;
FIG. 6 shows the results of example 2 under 278K, 298K, 308K ethylene solution (CuSiF)6)3(L1)4The isothermal adsorption-desorption curve diagram above;
FIG. 7 shows the reaction of propyne at 278K, 298K, 308K in example 2 under (CuSiF)6)3(L1)4The isothermal adsorption-desorption curve diagram above;
FIG. 8 shows propylene at 278K, 298K, 308K in example 2 under (CuSiF)6)3(L1)4The isothermal adsorption-desorption curve diagram above;
FIG. 9 shows the mixed gas of propyne/propylene and acetylene/ethylene in examples 1 to 3 (CuTiF)6)3(L1)4、(CuSiF6)3(L1)4、(CuNbOF5)3(L1)4Upper IAST selectivity graph.
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 following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Pillared anions (i.e., high coordination number inorganic anions) as used herein[ SiF ]6]2-、[TiF6]2-、[GeF6]2-、[NbOF5]2-、[B12H12]2-、[B10H10]2-The structure of (2) is shown in fig. 1.
Example 1
In a 50mL round bottom flask, 241.6mg (1mmol) of Cu (NO)3)2·3H2O and 197.9mg (1mmol) of (NH)4)2TiF6Dissolved in 14mL of water. In a further 50mL round-bottom flask 331.05mg (1.3mmol) of tris (4-pyridyl) amine (L1) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a purple solid precipitate, filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 120 ℃ for 10 hours to obtain the column cage type metal organic framework material (CuTiF) for gas separation6)3(L1)4。
FIG. 2 is (CuTiF)6)3(L1)4The structure is characterized in that copper is coordinated to four different pyridine rings in the horizontal direction and then infinitely extends to form a (3,4) -connected pto framework, and copper is coordinated to two different fluorines of hexafluorotitanate in the vertical direction. Each hexafluorotitanate connects two different copper, forming a (3,6) -connected ith-d framework.
Subjecting the activated material to 77K N under liquid nitrogen condition2And (4) performing adsorption-desorption experiments to obtain parameters such as specific surface area, pore volume and the like of the material. The results are shown in FIG. 3, (CuTiF)6)3(L1)4BET specific surface area of 1361.37m2Per g, pore volume 0.53cm3(ii) in terms of/g. Subsequently measured at 278K, 298K, 308K (CuTiF)6)3(L1)4The single-component adsorption curves of acetylene, ethylene, propyne and propylene are fitted and calculated based on an Ideal Adsorption Solution Theory (IAST) and adsorption data to obtain the separation selectivity of the single-component gas and the bi-component gas of propyne/propylene,wherein, as shown in FIG. 9, the selectivity of propyne/propylene (volume ratio 1:99) is as high as 13.08, which shows (CuTiF)6)3(L1)4The trace amount of propyne in the propyne/propylene mixed gas can be adsorbed, and high-selectivity separation is realized.
As shown in fig. 4, will (CuTiF)6)3(L1)4When the column cage type metal organic framework is filtered out from absolute methanol and soaked in water for one week, an XRD pattern is not changed, which shows that the water stability of the column cage type metal organic framework is good, and in addition, as shown in figure 4, the framework can still keep the original shape at 300 ℃, which shows that the thermal stability is good. Finally, as shown in FIG. 4, for (CuTiF)6)3(L1)4The cyclic adsorption-desorption determination of acetylene shows that the adsorption curve is not obviously changed, which indicates that the cyclic performance is good.
0.5g of (CuTiF)6)3(L1)4Grinding into fine powder with uniform size, placing into an adsorption column with inner diameter of 0.5cm and length of 5cm, introducing mixed gas of propyne/propylene into the adsorption column at room temperature of 25 deg.C at a rate of 1mL/min, wherein propylene penetrates earlier than propyne, and propyne penetrates out at 1064min after propylene comes out. Illustrates (CuTiF)6)3(L1)4The trace amount of propyne in the propyne/propylene mixed gas can be adsorbed, and high-selectivity separation is realized.
Example 2
277.7mg (1mmol) of CuSiF in a 50mL round-bottomed flask6Dissolved in 14mL of water. In a further 50mL round-bottom flask 331.05mg (1.3mmol) of tris (4-pyridyl) amine (L1) were dissolved in 30mL of methanol. Adding methanol solution dropwise into the water solution, stirring at 30 deg.C for 48 hr to obtain mauve solid precipitate, filtering, and washing with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 120 ℃ for 10 hours to obtain the column cage type metal organic framework material (CuSiF) for gas separation6)3(L1)4。
The single-component adsorption curves of acetylene, ethylene, propyne and propylene were measured at 278K, 298K and 308K for the activated material, and the results are shown in fig. 5 to 8. Then, based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting calculation, the separation selectivity of the catalyst on acetylene/ethylene and propyne/propylene of single-component gas and double-component gas is obtained, as shown in FIG. 9, the selectivity of acetylene/ethylene (volume ratio of 1:99) is as high as 11.15, and the selectivity of propyne/propylene (volume ratio of 1:99) is as high as 15.14.
Will (CuSiF)6)3(L1)4The structure of the column cage type metal organic framework is not changed after the column cage type metal organic framework is filtered out from absolute methanol and soaked in water for one week, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 250 ℃ through TGA analysis, which shows that the thermal stability is good.
Example 3
In a 50mL round-bottomed flask, 339.4mg (1mmol) of CuNbOF5Dissolved in 14mL of water. In a further 50mL round-bottom flask 331.05mg (1.3mmol) of tris (4-pyridyl) amine (L1) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a blue solid precipitate, filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 6 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 120 ℃ for 24 hours to obtain the column cage type metal organic framework material (CuNbOF) for gas separation5)3(L1)4。
The activated material is respectively measured for single-component adsorption curves of acetylene, ethylene, propyne and propylene under 278K, 298K and 308K, and then the separation selectivity of the activated material on single-component gas, bi-component gas of acetylene/ethylene and propyne/propylene is obtained by fitting calculation based on Ideal Adsorption Solution Theory (IAST) and adsorption data, as shown in FIG. 9, the selectivity of acetylene/ethylene (volume ratio of 1:99) is as high as 3.81, and the selectivity of propyne/propylene (volume ratio of 1:99) is as high as 17.69.
Will (CuNbOF)5)3(L1)4The column cage type metal organic framework is filtered out from absolute methanol and soaked in water for one month, the structure is not changed, the water stability of the column cage type metal organic framework is good, and in addition, the framework can be analyzed by TGAIt remained intact at 300 ℃ indicating good thermal stability.
Example 4
In a 50mL round-bottomed flask, 290.79mg (1mmol) of Ni (NO)3)2·6H2O and 212mg (1mmol) of Na2B12H12Dissolved in 14mL of water. In a further 50mL round-bottom flask 401.87mg (1.3mmol) of 1,3, 5-tris (pyridin-4-yl) benzene (L4) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a blue-green solid precipitate, filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 5 times to remove water molecules in the pores of the material, and then activating the material in vacuum at 80 ℃ for 10 hours to obtain the column cage type metal organic framework material (NiB) for gas separation12H12)3(L4)4。
After activation of (NiB)12H12)3(L4)4Single-component adsorption curves of propyne and propylene are measured at 298K, calculated by using Clausians-Clapeyron equation and fitted (NiB)12H12)3(L4)4Isothermal adsorption curves for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of bi-component gas propyne/propylene (volume ratio of 1:99) is as high as 13.41.
Will (NiB)12H12)3(L4)4The structure of the column cage type metal organic framework is not changed after filtering out from absolute methanol and soaking in water for one month, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 250 ℃ through TGA analysis, which shows that the thermal stability is good.
Example 5
In a 50mL round bottom flask, 241.6mg (1mmol) of Cu (NO)3)2·3H2O and 212mg (1mmol) of Na2B12H12Dissolved in 14mL of water. In a further 50mL round-bottom flask 344.84mg (1.3mmol) of tris (pyridin-4-yl) phosphine (L2) were dissolved in 30mL of methanol. Gradually adding methanol solutionDropwise adding into the water solution, stirring at 30 deg.C for 48 hr to obtain blue solid precipitate, filtering, and washing with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 75 ℃ for 10 hours to obtain the column cage type metal organic framework material (CuB) for gas separation12H12)3(L2)4。
Activating (CuB)12H12)3(L2)4Single-component adsorption curves of propyne and propylene are measured at 298K, calculated by using Clausians-Clapeyron equation and fitted to (CuB)12H12)3(L2)4Isothermal adsorption curves for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of bi-component gas propyne/propylene (volume ratio of 1:99) is as high as 15.23.
Will (CuB)12H12)3(L2)4The structure of the column cage type metal organic framework is not changed after filtering out from absolute methanol and soaking in water for one month, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 270 ℃ through TGA analysis, which shows that the thermal stability is good.
Example 6
In a 50mL round bottom flask, 297.49mg (1mmol) of Zn (NO)3)2·6H2O and 222.71mg (1mmol) of (NH)4)2GeF6Dissolved in 14mL of water. In a further 50mL round-bottom flask 318.62mg (1.3mmol) of tris (4-pyridyl) borane (L3) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give an off-white solid precipitate, filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 120 ℃ for 10 hours to obtain the column cage type metal organic framework material (ZnGeF) for gas separation6)3(L3)4。
Will aliveAfter conversion of (ZnGeF)6)3(L3)4Measuring single-component adsorption curves of propyne and propylene at 298K, calculating and fitting by using Clausians-Clapeyron equation (ZnGeF)6)3(L3)4Isothermal adsorption curves for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of bi-component gas propyne/propylene (volume ratio of 1:99) is as high as 5.73.
Will (ZnGeF)6)3(L3)4The structure of the column cage type metal organic framework is not changed after filtering out from absolute methanol and soaking in water for one month, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 230 ℃ through TGA analysis, which shows that the thermal stability is good.
Example 7
In a 50mL round bottom flask, 291.03mg (1mmol) of Co (NO)3)2·6H2O and 197.9mg (1mmol) of (NH)4)2TiF6Dissolved in 14mL of water. In a further 50mL round-bottom flask 406.34mg (1.3mmol) of 2,4, 6-tris (pyridin-4-yl) -1,3, 5-triazine (L6) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a pink solid precipitate, filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 120 ℃ for 10 hours to obtain the column cage type metal organic framework material (CoTiF) for gas separation6)3(L6)4。
After activation (CoTiF)6)3(L6)4Single-component adsorption curves of propyne and propylene are measured at 298K, calculated by using Clausians-Clapeyron equation and fitted to (CoTiF)6)3(L6)4Isothermal adsorption curves for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of bi-component gas propyne/propylene (volume ratio of 1:99) is as high as 6.01.
Will (CoTiF)6)3(L6)4From anhydrous methanolThe structure of the column cage type metal organic framework is not changed after the column cage type metal organic framework is soaked in water for one month, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 290 ℃ through TGA analysis, which shows that the thermal stability is good.
Example 8
In a 50mL round bottom flask, 241.6mg (1mmol) of Cu (NO)3)2·3H2O and 197.9mg (1mmol) of (NH)4)2TiF6Dissolved in 14mL of water. In a further 50mL round-bottom flask 324.4mg (1mmol) of tetrakis (pyridin-4-yl) methane (L7) were dissolved in 30mL acetonitrile. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a blue solid precipitate, filtered and washed with acetonitrile. Soaking the solid in anhydrous acetonitrile, replacing the anhydrous acetonitrile once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the material in vacuum at 80 ℃ for 10 hours to obtain the column cage type metal organic framework material (CuTiF) for gas separation6)(L7)。
After activation (CuTiF)6) (L7) Single-component adsorption curves of acetylene and ethylene were determined at 298K, calculated using the Clausians-Clapeyron equation and fitted to (CuTiF)6) (L7) isothermal adsorption curve for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of the bi-component gas acetylene/ethylene (volume ratio of 1:99) is as high as 10.01.
Will (CuTiF)6) (L7) the structure was not changed when it was soaked in water for one month after filtration from anhydrous methanol, indicating that the water stability of this column cage type metal organic framework was good, and further, the framework was maintained as it was at 300 ℃ by TGA analysis, indicating that the thermal stability was good.
Example 9
In a 50mL round bottom flask, 291.03mg (1mmol) of Co (NO)3)2·6H2O and 165mg (1mmol) of Na2B10H10Dissolved in 14mL of water. In a further 50mL round-bottomed flask 355.7mg (1.3mmol) of 1,3, 5-tris (1H-imidazol-1-yl) benzene (L5) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a pink solid precipitate, filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 75 ℃ for 10 hours to obtain the column cage type metal organic framework material (CoB) for gas separation10H10)3(L5)4。
After activation of (CoB)10H10)3(L5)4Single-component adsorption curves of propyne and propylene are measured at 298K, calculated by using Clausians-Clapeyron equation and fitted (CoB)10H10)3(L5)4Isothermal adsorption curves for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of bi-component gas propyne/propylene (volume ratio of 1:99) is as high as 13.43.
Will (CoB)10H10)3(L5)4The structure of the column cage type metal organic framework is not changed after filtering out from absolute methanol and soaking in water for one month, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 300 ℃ through TGA analysis, which shows that the thermal stability is good.
Example 10
In a 50mL round-bottom flask, 338.0mg (1mmol) of Fe (BF) was charged4)2·6H2O and 212mg (1mmol) of Na2B12H12Dissolved in 14mL of water. In a further 50mL round-bottom flask 355.7mg (1.3mmol) of 1,3, 5-tris (1H-imidazol-1-yl) benzene (L5) were dissolved in 30mL of methanol. The methanol solution was added dropwise to the aqueous solution, stirred at 30 ℃ for 48 hours to give a pale yellow solid precipitate, which was filtered and washed with methanol. Soaking the solid in anhydrous methanol, replacing the anhydrous methanol once every six hours for more than 3 times to remove water molecules in the pores of the material, and then activating the solid in vacuum at 75 ℃ for 10 hours to obtain the column cage type metal organic framework material (FeB) for gas separation12H12)3(L5)4。
After activation of (CoB)10H10)3(L5)4Single-component adsorption curves of propyne and propylene are measured at 298K, calculated by using Clausians-Clapeyron equation and fitted (CoB)10H10)3(L5)4Isothermal adsorption curves for the above gases. Based on Ideal Adsorption Solution Theory (IAST) and adsorption data fitting, the separation selectivity of bi-component gas propyne/propylene (volume ratio of 1:99) is as high as 11.23.
Will (CoB)10H10)3(L5)4The structure of the column cage type metal organic framework is not changed after filtering out from absolute methanol and soaking in water for one month, which shows that the water stability of the column cage type metal organic framework is good, and in addition, the framework can still keep the original shape at 240 ℃ through TGA analysis, which shows that the thermal stability is good.
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 (8)
1. A hydrothermally stable cylindrical cage type metal-organic framework material is characterized by being formed by self-assembly of metal ions M, nonlinear multidentate nitrogen-containing ligands L and high-coordination-number inorganic anions through coordination bonds;
the metal ion M is Cu2+、Ni2+、Fe2+、Co2+、Zn2+At least one of;
the nonlinear multidentate nitrogen-containing ligand L has a structure represented by any one of the following formulas L1 to L7:
the inorganic anion with high coordination number is SiF6 2-、TiF6 2-、GeF6 2-、NbOF5 2-Or a boron cage anion;
the boron cage anion has a structure represented by the following formula (I) or (II):
2. a method of preparing a hydrothermally stable column-cage metal organic framework material according to claim 1, comprising the steps of:
(1) dissolving a salt containing metal ions M and a high-coordination-number inorganic anion salt in deionized water to obtain a solution X, dissolving a nonlinear multidentate nitrogen-containing ligand L in an organic solvent A to obtain a solution Y, dropwise adding the solution X into the solution Y, stirring for 24-72 h at 25-100 ℃, carrying out solid-liquid separation, and washing the obtained solid with the deionized water and the organic solvent A to obtain an intermediate product;
the organic solvent A is at least one of methanol, ethanol, acetone and acetonitrile;
(2) and soaking the intermediate product in an organic solvent A to displace and remove water molecules in the pore channels, wherein the displacement time is 5-12 h each time, displacing 3-6 times, and then vacuumizing, degassing and activating for 10-24 h at 75-120 ℃ to obtain the hydrothermally stable column cage type metal organic framework material.
3. The production method according to claim 2, wherein in the step (1), the salt containing the metal ion M is a nitrate and/or a tetrafluoroborate of the metal ion M.
4. The method according to claim 2, wherein in the step (1), the salt of the high-coordination-number inorganic anion is a sodium salt and/or an ammonium salt of the high-coordination-number inorganic anion.
5. The production method according to claim 2, wherein in step (1), the salt containing the metal ion M, the salt of the high-coordination-number inorganic anion, and the nonlinear multidentate nitrogen-containing ligand L are added in a molar ratio of the metal ion M, the high-coordination-number inorganic anion, and the nonlinear multidentate nitrogen-containing ligand L of 3:3:4 or 1:1: 1.
6. Use of the hydrothermally stable column cage metal organic framework material of claim 1 in the field of selective adsorption separation of gases.
7. The use according to claim 6, wherein the hydrothermally stable cylindrical cage metal organic framework material is used for acetylene/ethylene selective adsorption separation.
8. The use according to claim 6, wherein the hydrothermally stable cylindrical cage metal organic framework material is used for selective adsorptive separation of propyne/propylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114669163A (en) * | 2022-03-23 | 2022-06-28 | 浙江师范大学 | Method for capturing carbon dioxide from flue gas |
| CN114890863A (en) * | 2022-06-09 | 2022-08-12 | 浙江师范大学 | Method for separating and purifying ethylene |
| CN116554492A (en) * | 2023-05-17 | 2023-08-08 | 浙江师范大学 | Ion hybridization hierarchical pore metal organic framework material with wly topological structure and preparation and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114669163A (en) * | 2022-03-23 | 2022-06-28 | 浙江师范大学 | Method for capturing carbon dioxide from flue gas |
| CN114890863A (en) * | 2022-06-09 | 2022-08-12 | 浙江师范大学 | Method for separating and purifying ethylene |
| CN114890863B (en) * | 2022-06-09 | 2023-07-18 | 浙江师范大学 | Method for separating and purifying ethylene |
| CN116554492A (en) * | 2023-05-17 | 2023-08-08 | 浙江师范大学 | Ion hybridization hierarchical pore metal organic framework material with wly topological structure and preparation and application thereof |
| CN116554492B (en) * | 2023-05-17 | 2024-02-20 | 浙江师范大学 | Ion hybridization hierarchical pore metal organic framework material with wly topological structure and preparation and application thereof |
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