CN112538168B - Iron metal organic framework material based on eight-head ligand, preparation method and hydrogen storage application thereof - Google Patents
Iron metal organic framework material based on eight-head ligand, preparation method and hydrogen storage application thereof Download PDFInfo
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Abstract
An iron metal-organic framework material based on eight ligands, a preparation method thereof and hydrogen storage performance research belong to the technical field of crystalline materials. Chemical formula is [ Fe4(μ2‑OH)4(TCTA)]，H8TCTA is an octameric carboxylic acid organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid. The synthesis of the metal-organic framework is carried out under a closed condition, and an organic ligand 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H) is8TCTA) and ferric nitrate in a mixed solution of N, N-dimethylformamide and water, and obtaining a crystal of the metal organic framework material through a solvothermal reaction; the metal-organic framework material exhibits hydrogen adsorption properties.
Description
Technical Field
The invention belongs to the technical field of crystalline materials, and relates to a metal-organic coordination polymer material, which is characterized by a metal-organic framework material of iron, a preparation method and hydrogen storage performance research thereof.
Background
Metal-Organic Frameworks (MOFs) are formed by connecting inorganic nodes formed by Metal ions/clusters and Organic ligands through coordination bonds. As a novel organic-inorganic porous material, MOFs has the characteristics of large specific surface area, high porosity, adjustable porosity and the like. In recent years, MOFs have potential applications in a variety of fields such as adsorption/separation, sensing, heterogeneous catalysis, and the like.
Due to the low density of hydrogen, it is difficult to store hydrogen, and it is necessary to compress hydrogen gas at a high pressure of 700 bar. There is currently a great deal of research on the storage of hydrogen at relatively low pressures for conventional porous adsorbent materials (e.g., zeolites, etc.) and emerging porous materials (e.g., MOFs, etc.). MOFs are highly tunable in surface area, pore size, pore shape, and functional site, and exhibit great potential in gas storage and separation. With MOFs, dense packing of hydrogen can be achieved.
Disclosure of Invention
The invention aims to provide an iron metal organic framework material based on eight ligands, a preparation method thereof and hydrogen storage performance research.
The invention relates to an iron metal-organic framework material based on eight-head carboxylic acid ligand, which is characterized in that the chemical molecular formula is [ Fe ]4(μ2-OH)4(TCTA)]，H8TCTA is an octameric carboxylic acid organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid.
From the viewpoint of frame connection construction, the crystal structure of the metal-organic frame belongs to an orthorhombic system, the space group is Ibam, and the unit cell parameters are as follows: a is 12.3404(4),
α＝β＝γ＝90°。
in the metal-organic framework, the asymmetric unit of the crystal comprises 1/4 TCTAs8-Ligand, 2 Fe atoms and 3O atoms. Each Fe atom is derived from 4 different TCTAs in octahedral configuration8-Carboxyl O atom of ligand and 2. mu2-OH coordination; adjacent Fe atoms being bridgedMu of2-OH and TCTA8-The carboxyl groups bridged on the ligand form a one-dimensional chain Secondary Building Unit (SBU) [ Fe (mu) ]2-OH)(COO)2]。
In the metal-organic framework, the Fe-O bond has a length of
Within the range. TCTA8-Four carbazole groups in the ligand are vertical to a central benzene ring, and an included angle between two carboxyl groups on each carbazole group is 90 degrees. Each TCTA8-The ligand is connected with 8 Fe atoms respectively positioned on four chain SBUs, and each Fe atom is connected with 4 different TCTAs8-And connecting the ligands to form a three-dimensional framework structure with one-dimensional diamond and square pore channels.
The synthesis method of the metal-organic framework material comprises the following steps:
2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid (H) under sealed conditions8TCTA) and ferric nitrate (Fe (NO)3)2·9H2O) in a mixed solution of N, N-Dimethylformamide (DMF) and deionized water, and obtaining the crystal of the metal-organic framework through solvothermal reaction.
Further preferred is the organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid (H)8TCTA) and ferric nitrate in a molar ratio of 1 (1-6), wherein each 0.01mmol of ferric nitrate corresponds to 1-4 mL of DMF and 0.1-4 mL of deionized water, the temperature of the thermal reaction is 100-160 ℃, and the reaction time is 12-60 hours.
The metal-organic framework has better stability and higher specific surface area, so that the MOFs have potential application in the aspect of hydrogen storage.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of an eight-head carboxylic acid ligand for the synthesis of the metal-organic framework.
FIG. 2 is a diagram of the inorganic building blocks in the metal-organic framework.
Fig. 3 is a schematic three-dimensional structure diagram of the metal-organic framework.
Fig. 4 is a schematic diagram of nitrogen adsorption of the metal-organic framework.
Fig. 5 is a hydrogen sorption isotherm diagram of the metal-organic framework material.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
weighing ligand H8TCTA (0.01mmol) and Fe (NO)3)2·9H2O (0.02mmoL) was placed in a 25mL beaker, 3mL of DMF solution and 0.1mL of deionized water were added, the beaker was sealed and placed in an ultrasonic apparatus, and ultrasonic treatment was performed at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction vessel. After sealing, the reaction kettle is placed in an oven at 120 ℃ for reaction for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give tan block crystals (Fe)4(μ2-OH)4(TCTA)), (yield: 36% based on H8TCTA ligand).
Example 2:
weighing ligand H8TCTA (0.02mmol) and Fe (NO)3)2·9H2O (0.02mmoL) was placed in a 25mL beaker, 6mL of DMF solution and 0.15mL of deionized water were added, the beaker was sealed and placed in an ultrasonic apparatus, and ultrasonic was applied at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction kettle. After sealing, the reaction kettle is placed in an oven at 120 ℃ for reaction for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give tan block crystals (Fe)4(μ2-OH)4(TCTA)), (yield: 45% based on H8TCTA ligand).
Example 3
Weighing ligand H8TCTA (0.02mmol) and Fe (NO)3)2·9H2O (0.04mmoL) was placed in a 25mL beaker, 6mL of DMF solution and 0.2mL of deionized water were added, the beaker was sealed and placed in an ultrasonic apparatus, sonicated at room temperature for 5 minutes, and after completion the solution was transferred to a 20mL Teflon reaction kettle. After sealing, the reaction kettle is placed in an oven at 150 ℃ for reaction for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give tan block crystals (Fe)4(μ2-OH)4(TCTA)), (yield: 49% based on H8TCTA ligand).
Example 4
Weighing ligand H8TCTA (0.05mmol) and Fe (NO)3)2·9H2O (0.12mmoL) was placed in a 25mL beaker, 10mL of DMF solution and 1mL of deionized water were added, the beaker was sealed and placed in an ultrasonic apparatus, and ultrasonic was applied at room temperature for 5 minutes, after which the solution was transferred to a 20mL Teflon reaction vessel. After sealing, the reaction kettle is placed in an oven at 150 ℃ for reaction for 24 hours. After the reaction is finished, the drying oven is closed, the reaction kettle is opened after the reaction kettle is cooled to room temperature, solid particles obtained in the reaction kettle are filtered and collected, and then DMF and H are sequentially used2Washed with O and EtOH (5 mL. times.3) and observed under a microscope to give tan block crystals (Fe)4(μ2-OH)4(TCTA)), (yield: 57% based on H8TCTA ligand).
The test results of the products obtained in the above examples are the same, and specifically the following are given:
(1) determination of crystal structure:
selecting a single crystal sample with a proper size, and collecting data by using a Rigaku Supernova single crystal instrument under the condition of 100K. Data collection using monochromatization by graphite monochromators
A target ray. Data absorption correction was done using SCALE3 absack software. The crystal structure was resolved by direct methods using the program SHELXTL-97. First using a difference function and a minimum of twoMultiplying to determine all non-hydrogen atom coordinates, obtaining hydrogen atom position by theoretical hydrogenation method, and refining crystal structure by SHELXTL-97. The structure is shown in fig. 2 to 3. The crystallographic data are shown in table 1.
TABLE 1 crystallography data for metal organic framework materials
The eight head carboxylic acid ligand synthesis scheme of FIG. 1 shows: firstly, adding 3, 6-dibromo-9H-carbazole and p-methoxycarbonyl phenylboronic acid into ethylene glycol dimethyl ether and water, adding potassium carbonate and tetrakis (triphenylphosphine) palladium, heating to 60-100 ℃ to react under the protection of sealing and inert gas to obtain dimethyl 4,4' - (9H-carbazole-3, 6-diyl) dibenzoate; dispersing dimethyl 4,4'- (9H-carbazole-3, 6-diyl) dibenzoate in tetrahydrofuran solution, adding sodium hydride, adding 2,3,5, 6-tetrafluoroterephthalonitrile, and reacting at room temperature to obtain octamethyl 4,4' - ((3, 6-terephthalonitrile-1, 2,4, 5-diyl) tetra (9H-carbazole-9, 3, 6-triyl)) octabenzoate; heating, refluxing and deprotecting octamethyl 4,4' ((3, 6-terephthalonitrile-1, 2,4, 5-tetra-yl) tetra (9H-carbazole-9, 3, 6-tri-yl)) octabenzoate and sodium hydroxide in a tetrahydrofuran/methanol/water mixed solution to obtain 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H-carbazole-9-yl) terephthalic acid8TCTA)
The block diagram of fig. 2 shows: the inorganic nodes contained in the frame structure are chain SBU [ Fe (mu) ]2-OH)(COO)2]。
The block diagram of fig. 3 shows: a three-dimensional stacking diagram on the metal-organic framework.
The block diagram of fig. 4 shows: the nitrogen adsorption diagram of the metal-organic framework material shows that the metal-organic framework has higher specific surface area.
(2) Hydrogen adsorption
Fig. 5 is a hydrogen sorption isotherm of the material of the invention, which can be seen to be effective for hydrogen sorption. FIG. 5 is a hydrogen sorption isotherm of the material of the invention under liquid nitrogen conditions at 77K, as measured by a gas sorption instrument.
Claims (6)
1. An iron metal-organic framework material based on eight-head carboxylic acid ligands, characterized in that the chemical formula is [ Fe ]4(μ2-OH)4(TCTA)]，H8TCTA is octameric carboxylic acid organic ligand 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid;
the preparation method comprises the following steps: 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid (H) under sealed conditions8TCTA) and iron nitrate Fe (NO)3)2·9H2Obtaining the crystal of the metal-organic framework through solvothermal reaction of O in a mixed solution of N, N-Dimethylformamide (DMF) and deionized water; wherein the organic ligand 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H)8TCTA) and ferric nitrate, wherein the molar ratio of the TCTA) to the ferric nitrate is 1 (1-6), each 0.01mmol of ferric nitrate corresponds to 1-4 mL of DMF, 0.1-4 mL of deionized water, the temperature of thermal reaction is 100-160 ℃, and the reaction time is 12-60 hours.
2. The iron metal-organic framework material based on eight-head carboxylic acid ligands according to claim 1, characterized in that the crystal structure of the metal-organic framework belongs to the orthorhombic system from the viewpoint of framework connection construction, the space group is Ibam, and the unit cell parameters are: a is 12.3404(4),
α＝β＝γ＝90°。
3. the metal-organic framework material of iron based on octameric carboxylic acid ligands according to claim 1, characterized in that the asymmetric units of the metal-organic framework crystal structure comprise 1/4 TCTA8-Ligand, 2 Fe atoms and 3O atoms; each Fe atom is derived from 4 different TCTAs in octahedral configuration8-Carboxyl O atom of ligand and 2. mu.2-OH coordination; adjacent Fe atom throughOverbridged mu2-OH and TCTA8-Carboxyl groups bridged on the ligand form a one-dimensional chain-shaped secondary construction unit [ Fe (mu) ]2-OH)(COO)2]。
4. A metal-organic framework material of iron based on eight head carboxylic acid ligands according to claim 1, characterized in that in the metal-organic framework the Fe-O bonds are longer than
Within the range; TCTA8-Four carbazole groups in the ligand are perpendicular to a central benzene ring, and an included angle between two carboxyl groups on each carbazole group is 90 degrees; each TCTA8-The ligand is connected with 8 Fe atoms respectively positioned in four chain SBUs, and each Fe atom is connected with 4 different TCTAs8-And connecting the ligands to form a three-dimensional framework structure with one-dimensional diamond and square pore channels.
5. The method for preparing an iron metal-organic framework material based on eight-head carboxylic acid ligands as claimed in claim 1, wherein 2,3,5, 6-tetrakis (3, 6-bis (4-carboxyphenyl) -9H-carbazol-9-yl) terephthalic acid (H) is prepared under sealed conditions8TCTA) and iron nitrate Fe (NO)3)2·9H2Obtaining the crystal of the metal-organic framework through solvothermal reaction of O in a mixed solution of N, N-Dimethylformamide (DMF) and deionized water; wherein the organic ligand 2,3,5, 6-tetra (3, 6-bis (4-carboxyphenyl) -9H-carbazole-9-yl) terephthalic acid (H)8TCTA) and ferric nitrate, wherein the molar ratio of the TCTA) to the ferric nitrate is 1 (1-6), each 0.01mmol of ferric nitrate corresponds to 1-4 mL of DMF, 0.1-4 mL of deionized water, the temperature of thermal reaction is 100-160 ℃, and the reaction time is 12-60 hours.
6. Use of an iron metal-organic framework material based on eight head carboxylic acid ligands according to claim 1 as adsorbent for hydrogen storage.
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