Method for producing metal-organic framework

Abstract

To provide a method for producing a metal-organic framework by which the metal-organic framework excellent in handleability can be obtained.SOLUTION: A method for producing a metal-organic framework containing a metal ion and an organic ligand by a solution method, the method comprising: preparing a solution containing a metal ion and an organic compound in a container; and rotating the container such that a rotation axis is less than 90 ° with respect to a liquid surface of the solution.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a metal-organic framework. [Background technology]

[0002] A solution synthesis method is a method for producing a metal organic framework. The solution synthesis method is a method for producing a metal organic framework by mixing and stirring a solution containing metal ions and a solution containing an organic compound that serves as an organic ligand. For example, a method for producing a metal organic framework by mixing and stirring a solution containing a copper compound and a solution containing an organic ligand is known (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2009-526011 Summary of the Invention [Problem to be solved by the invention]

[0004] With the method described in Patent Document 1, it was difficult to obtain a metal-organic framework that was easy to handle. [Means for solving the problem]

[0005] The method for producing a metal organic framework of the present disclosure is a method for producing a metal organic framework containing metal ions and organic ligands by a solution process, and includes preparing a solution (A) containing metal ions and organic ligands in a container, and rotating the container so that the rotation axis is at an angle of less than 90° with respect to the liquid surface of the solution (A). [Effects of the Invention]

[0006] According to the present disclosure, there is provided a production method that can produce an organic structure with excellent handleability in high yield. DETAILED DESCRIPTION OF THE INVENTION

[0007] The manufacturing method according to the present disclosure will be described below.

[0008] The method for producing an organic framework according to the present disclosure is a method for producing a metal-organic framework containing metal ions and organic ligands by a solution process, comprising the steps of: (i) preparing a solution (A) containing metal ions and an organic ligand in a container; (ii) rotating the container so that the rotation axis is at an angle of less than 90° with respect to the liquid surface of the solution (A); Includes.

[0009] In the production method of the present disclosure, a metal-organic framework with excellent handleability can be obtained by rotating the reaction vessel itself in the solution method. Specifically, the metal-organic framework can be obtained as a powder with a small angle of repose and a large bulk density. Furthermore, the metal-organic framework obtained by the production method of the present disclosure has a large particle size. Furthermore, the metal-organic framework obtained by the production method of the present disclosure has low adhesion to the inside of the vessel and is easy to handle. The production method of the present disclosure in which the reaction is carried out while rotating the vessel is also referred to as a "rotation method."

[0010] The solution method is a method in which a metal organic framework is obtained by reacting a metal ion with an organic ligand in a solution.

[0011] (i) preparing a solution (A) containing metal ions and an organic ligand in a container; Solution (A) is a reaction solution for the metal organic framework.

[0012] The metal ion is not particularly limited as long as it can constitute a metal organic framework, and is, for example, an ion of a metal selected from Zr, Zn, Mn, Cu, Co, Fe, and Al. The metal ion is preferably a copper (II) ion.

[0013] The source of the metal ions is preferably a metal salt. That is, the metal ions are generated by dissolving a metal salt in a solvent. The metal salt is preferably an inorganic salt. The inorganic salt is preferably a formate, acetate, nitrate, sulfate, carbonate, or tartrate of a metal selected from Zr, Zn, Mn, Cu, Co, Fe, and Al, and is preferably a nitrate.

[0014] In a preferred embodiment, the metal ion is a copper (II) ion, and the copper ion source is an inorganic salt of copper, preferably copper (II) nitrate. By using copper (II) nitrate, the yield can be improved and a metal-organic framework with a large particle size can be obtained.

[0015] The concentration of the metal ions in the solution (A) is preferably 0.1 mol / l or more and 1.0 mol / l or less, more preferably 0.2 mol / l or more and 0.8 mol / l or less.

[0016] The organic ligand is not particularly limited as long as it can be coordinated to the metal ion. The organic ligand is preferably a ligand having two or more and four or less carboxylic acids, more preferably a tricarboxylic acid or tetracarboxylic acid, and even more preferably a tricarboxylic acid. Specific examples of the organic ligand include terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, and 4,4'-diphenyldicarboxylic acid. Benzenetricarboxylic acid is preferred, and 1,3,5-benzenetricarboxylic acid (trimesic acid) is more preferred.

[0017] The concentration of the organic ligand in the solution (A) is preferably 0.07 mol / l or more and 0.7 mol / l or less, more preferably 0.13 mol / l or more and 0.53 mol / l or less.

[0018] The molar ratio of organic ligands to metal ions in solution (A) (organic ligands / metal ions) is preferably 0.3 or more and 2 or less, more preferably 0.5 or more and 1 or less.

[0019] In a preferred embodiment, the metal ion is a copper (II) ion and the organic ligand is 1,3,5-benzenetricarboxylic acid. The organic framework composed of copper (II) ions and 1,3,5-benzenetricarboxylic acid is also called HKUST-1.

[0020] The solvent for solution (A) is preferably water or an alcohol, or a mixture thereof.

[0021] The alcohol may be, for example, C 1-4 The alcohol is preferably methanol or ethanol.

[0022] The volume ratio of water to alcohol (water / alcohol) in the solution (A) is preferably 0.25 or more and 4 or less, more preferably 0.5 or more and 2 or less, and even more preferably 0.65 or more and 1.5 or less.

[0023] The solution (A) may further contain a base.

[0024] The base may be an organic base or an inorganic base.

[0025] Examples of the inorganic base include hydroxides or carbonates of alkali metals or alkaline earth metals, and ammonia.

[0026] Examples of the organic base include amine compounds, amide compounds, and pyridine compounds. The organic base is preferably N,N-diethylformamide or N,N-dimethylformamide, and more preferably N,N-dimethylformamide. By using such an organic base, particularly N,N-dimethylformamide, the metal organic structure can be obtained in good yield.

[0027] The content of the base in solution (A) is preferably 0.01 or more and 100 or less, more preferably 0.02 or more and 50 or less, even more preferably 0.1 or more and 1 or less, and even more preferably 0.2 or more and 1 or less, in terms of volume ratio to the solvent (base / solvent).

[0028] Solution (A) may be obtained by dissolving the metal salt and the organic ligand in a solvent, or by preparing a solution of the metal salt and a solution of the organic ligand separately and then mixing them. Alternatively, a solution of either the metal salt or the organic ligand may be directly mixed with the other.

[0029] Preferably, solution (B) containing the metal salt and solution (C) containing the organic ligand are separately prepared and then mixed in a container to prepare solution (A).

[0030] Solution (B) can be obtained by dissolving a metal ion source, typically a metal salt, in a solvent, which can be water or an alcohol, or a mixture thereof, preferably water.

[0031] The content of metal ions in solution (B) is preferably 0.01 mol / l or more and 10 mol / l or less, more preferably 0.1 mol / l or more and 6.0 mol / l or less, and even more preferably 0.4 mol / l or more and 3.0 mol / l or less.

[0032] The solution (C) can be obtained by dissolving the organic ligand in a solvent, which is water or an alcohol, or a mixture thereof, preferably an alcohol, more preferably methanol or ethanol.

[0033] The content of the organic ligand in solution (C) is preferably 0.01 mol / l or more and 10 mol / l or less, more preferably 0.05 mol / l or more and 5.0 mol / l or less, and even more preferably 0.1 mol / l or more and 1.0 mol / l or less.

[0034] The base may be contained in either or both of solution (B) and solution (C). Preferably, the base is contained in solution (C).

[0035] (ii) rotating the container so that the rotation axis is less than 90° relative to the liquid surface of the solution (A); By rotating the container containing solution (A), solution (A) adhering to the wall of the container is raised above the liquid surface. That is, solution (A) can exist as a thin film on the wall of the container above the liquid surface. This allows nucleation and self-assembly of the metal-organic framework to occur quickly, improving the yield and promoting self-assembly, thereby enabling the production of a metal-organic framework with large crystals that are easy to handle.

[0036] The container is not particularly limited as long as it has a shape that allows it to be rotated, but preferably has a shape in which the cross section perpendicular to the axis of rotation is circular. Here, "circular" is not limited to a perfect circle, but may be any shape surrounded by smooth curves, and includes, for example, an ellipse. The cross section is preferably a substantially perfect circle. When the container has such a shape, a thin film of solution (A) is formed evenly on the wall surface of the container, and variation in size of the metal-organic framework can be reduced.

[0037] The material of the container is not particularly limited, but is preferably metal or glass.

[0038] The vessel is preferably a vessel having a circular cross section, such as an eggplant-shaped vessel or a round-bottom vessel. The vessel may also be a flask.

[0039] The method of rotating the container can be carried out using a commercially available rotary evaporator.

[0040] The rotation axis of the container is at an angle of less than 90° relative to the liquid surface of solution (A), preferably 10° to 80°, more preferably 10° to 60°, even more preferably 10° to 45°, and even more preferably 15° to 30°. By reducing the angle of the rotation axis relative to the liquid surface, more of solution (A) can be made into a thin film on the inner wall of the container. In other words, the area of ​​the thin film of solution (A) above the liquid surface can be increased. This improves the reaction rate and the yield.

[0041] The rotation speed of the container is preferably 10 rpm or more and 300 rpm or less, more preferably 20 rpm or more and 200 rpm or less, and even more preferably 30 rpm or more and 100 rpm or less. By setting the rotation speed in this range, the yield of the metal-organic framework is improved and the variation in particle size is also reduced.

[0042] The rotation speed of the container is such that the time during which any point on the inner wall is above the liquid surface of the solution (A) is preferably 0.1 to 3 seconds, more preferably 0.1 to 1 second.

[0043] The temperature of the solution (A) during rotation is preferably 40° C. or higher and 100° C. or lower, more preferably 60° C. or higher and 100° C. or lower. By setting the temperature in this range, the yield of the metal organic framework is improved.

[0044] The resulting metal-organic framework may then be filtered, washed, and dried.

[0045] The filtration may be carried out by a conventional filtration method, such as pressure filtration, reduced pressure filtration, or flat surface filtration, with flat surface filtration being industrially preferred.

[0046] The washing is preferably carried out with water or alcohol. Specifically, the washing solvent is, for example, water, methanol, ethanol, or a mixture thereof, with methanol and ethanol being preferred. The washing may be carried out simultaneously with the filtration.

[0047] Drying is preferably carried out at a high temperature under reduced pressure, preferably at 60°C or higher, more preferably at 80°C or higher and 200°C or lower, and even more preferably at 100°C or higher and 150°C or lower.

[0048] The particle size of the obtained metal-organic framework is preferably 10 μm or more, more preferably 15 μm or more, even more preferably 20 μm or more, and even more preferably 40 μm or more. The particle size may be, for example, 200 μm or less or 100 μm or less. Here, the particle size can be determined from a scanning electron microscope (SEM) image. Specifically, a representative particle is selected from the SEM image, and the maximum length of the straight line connecting any two perimeter points is taken as the particle size.

[0049] The specific surface area of ​​the resulting metal organic framework is preferably 1,700 m 2 / g or more, preferably 1,800m 2 / g or more.

[0050] The angle of repose of the resulting metal organic framework obtained by the injection method is preferably 45° or less, more preferably 40° or less.

[0051] The angle of repose of the resulting metal-organic framework, as measured by the tilt method, is preferably less than 40°, more preferably 35° or less, and even more preferably 30° or less. [Example]

[0052] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0053] (Example 1: Rotation Method) A 1-L eggplant-shaped flask was charged with a mixed solvent of 180 ml of ethanol and 180 ml of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 147 ml of pure water was added to the resulting trimesic acid solution to obtain solution (A). The resulting solution (A) was charged into an eggplant-shaped flask, heated to 60°C in an oil bath, and rotated in a rotary evaporator (50 rpm). The angle of the rotation axis relative to the liquid surface was 30°. After 24 hours of rotation, the resulting blue crystals were filtered using a Buchner funnel to obtain a filter cake. The filter cake was immersed in 500 ml of ethanol, washed, and then separated. The same procedure was repeated twice to obtain a separated cake. The resulting separated cake was blue crystals and had excellent filterability. The obtained crystals were vacuum dried at 150°C for 10 hours. The dry weight was 16.2g, and the yield per copper was 95%. The dried crystals had good fluidity without adhering to the container. Chemical analysis of the obtained crystals revealed that the Cu content was 31.1% (purity 98.7%) and the C content was 35.4% (purity 99.0%).

[0054] (Example 2: Rotation Method) A 300 L eggplant-shaped flask was charged with a mixed solvent of 36 mL of ethanol and 43 mL of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 30 mL of pure water was added to the resulting trimesic acid solution. The resulting solution (A) was charged into an eggplant-shaped flask, heated to 80 °C in an oil bath, and rotated in a rotary evaporator (50 rpm). The angle of the rotation axis relative to the liquid surface was 30°. After 24 hours of rotation, the resulting blue crystals were filtered using a Buchner funnel to obtain a filter cake. The filter cake was immersed in 200 mL of ethanol, washed, and then separated. The same procedure was repeated twice to obtain a separated cake. The resulting separated cake was blue crystals and had excellent filterability. The obtained crystals were vacuum dried at 150°C for 10 hours. The dry weight was 15.7g, and the yield per copper was 92%. The dried crystals also had good fluidity with no adhesion to the container. Chemical analysis of the obtained crystals revealed a Cu content of 30.9% (purity 98.0%) and a C content of 35.4% (purity 99.0%).

[0055] (Example 3: Rotation Method) A 300 L eggplant-shaped flask was charged with a mixed solvent of 36 mL of methanol and 43 mL of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid. This solution was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 30 mL of pure water was added to the resulting trimesic acid solution. The resulting solution (A) was charged into an eggplant-shaped flask, heated to 80°C in an oil bath, and rotated in a rotary evaporator (50 rpm). The angle of the rotation axis relative to the liquid surface was 30°. After 24 hours of rotation, the resulting blue crystals were filtered using a Buchner funnel to obtain a filter cake. The filter cake was immersed in 200 mL of methanol, washed, and then separated. This procedure was repeated twice to obtain a separated cake. The resulting separated cake was blue crystals with excellent filterability. The obtained crystals were vacuum dried at 150°C for 10 hours. The dry weight was 16.1g, and the yield per copper was 94%. The dried crystals also had good fluidity with no adhesion to the container. Chemical analysis of the obtained crystals revealed a Cu content of 30.9% (purity 98.0%) and a C content of 35.2% (purity 98.6%).

[0056] (Example 4: Rotation Method) A 300 L eggplant-shaped flask was charged with a mixed solvent of 36 mL of methanol and 43 mL of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid. This solution was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 30 mL of purified water was added to the resulting trimesic acid solution. The resulting solution (A) was charged into an eggplant-shaped flask, heated to 90°C in an oil bath, and rotated in a rotary evaporator (50 rpm). The angle of the rotation axis relative to the liquid surface was 30°. After 24 hours of rotation, the resulting blue crystals were filtered using a Buchner funnel to obtain a filter cake. The filter cake was immersed in 200 mL of methanol, washed, and then separated. This procedure was repeated twice to obtain a separated cake. The resulting separated cake was blue crystals with excellent filterability. The obtained crystals were vacuum dried at 150°C for 10 hours. The dry weight was 16.4g, and the yield per copper was 96%. The dried crystals also had good fluidity with no adhesion to the container. Chemical analysis of the obtained crystals revealed a Cu content of 30.9% (purity 99.6%) and a C content of 35.2% (purity 98.6%).

[0057] (Example 5: Rotation Method) A 300 L eggplant-shaped flask was charged with a mixed solvent of 36 mL of methanol and 43 mL of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid. This solution was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 30 mL of pure water was added to the resulting trimesic acid solution. The resulting solution (A) was charged into an eggplant-shaped flask, heated to 100 °C in an oil bath, and rotated in a rotary evaporator (50 rpm). The angle of the rotation axis relative to the liquid surface was 30°. After 24 hours of rotation, the resulting blue crystals were filtered using a Buchner funnel to obtain a filter cake. The filter cake was immersed in 200 mL of methanol, washed, and then separated. This procedure was repeated twice to obtain a separated cake. The resulting separated cake was blue crystals with excellent filterability. The obtained crystals were vacuum dried at 150°C for 10 hours. The dry weight was 16.4g, and the yield per copper was 96%. The dried crystals also had good fluidity with no adhesion to the container. Chemical analysis of the obtained crystals revealed a Cu content of 31.7% (purity 100.6%) and a C content of 35.56% (purity 99.5%).

[0058] (Comparative Example 1: Stirring method) A 500 ml flask was charged with 11.9 g (0.0566 mol) of trimesic acid and a mixed solvent of 180 ml of ethanol and 180 ml of dimethylformamide. This resulted in a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 147 ml of purified water was added to the resulting trimesic acid solution. The resulting solution was heated to 60°C and stirred with a rotor. After stirring for 24 hours, the resulting product was filtered through a Buchner funnel to obtain a filter cake. The filter cake was immersed in 500 ml of ethanol, washed, and then separated. This procedure was repeated twice to obtain a separated cake. The separated cake consisted of blue fine crystals and was vacuum dried at 150°C for 10 hours. The dry weight was 13.0 g, representing a yield of 76% based on copper. The product adhered to the inner wall of the flask, weighing 0.312 g. Chemical analysis of the obtained crystals revealed that the Cu content was 31.8% (purity 100.6%) and the C content was 35.2% (purity 98.5%).

[0059] (Comparative Example 2: Diffusion Method) A 500 ml flask was charged with a mixed solvent of 180 ml of ethanol and 180 ml of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 147 ml of purified water was added to the obtained trimesic acid solution. The obtained solution was heated to 60 °C and maintained at this temperature for 24 hours. The obtained product was filtered through a Buchner funnel to obtain a filter cake. The filter cake was immersed in 500 ml of ethanol, washed, and then separated. The same procedure was repeated twice to obtain a separated cake. The obtained separated cake consisted of blue fine crystals and was vacuum dried at 150 °C for 10 hours. The dry weight was 8.9 g, and the yield per copper was 52%. The product adhered to the inner wall of the flask, with the amount of adhesion being 0.329 g. Chemical analysis of the obtained crystals revealed that the Cu content was 31.4% (purity 99.6%) and the C content was 35.2% (purity 98.5%).

[0060] (Comparative Example 3: Stirring method) A 200 L flask was charged with a mixed solvent of 36 ml of methanol and 43 ml of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 30 ml of purified water was added to the resulting trimesic acid solution. The resulting solution was heated to 80 °C and stirred with a rotor. After stirring for 24 hours, the resulting product was filtered through a Buchner funnel to obtain a filter cake. The filter cake was immersed in 200 ml of ethanol, washed, and then separated. This procedure was repeated twice to obtain a separated cake. The separated cake consisted of blue fine crystals and was vacuum dried at 150 °C for 10 hours. The dry weight was 15.7 g, representing a yield per copper of 92%. Note that the product adhered to the inner wall of the flask in an amount of 0.215 g. Chemical analysis of the obtained crystals revealed that the Cu content was 32.1% (purity 101.8%) and the C content was 35.2% (purity 98.5%).

[0061] (Comparative Example 4: Diffusion Method) A 200 L flask was charged with a mixed solvent of 36 ml of methanol and 43 ml of dimethylformamide, and 11.9 g (0.0566 mol) of trimesic acid was dissolved to obtain a trimesic acid solution. Next, a solution of 20.5 g (0.0849 mol) of copper nitrate hexahydrate and 30 ml of pure water was added to the resulting trimesic acid solution. The resulting solution was heated to 80 °C and maintained at this temperature for 24 hours. The resulting product was filtered through a Buchner funnel to obtain a filter cake. The filter cake was immersed in 200 ml of ethanol, washed, and then separated. This procedure was repeated twice to obtain a separated cake. The separated cake consisted of blue fine crystals and was vacuum dried at 150 °C for 10 hours. The dry weight was 15.9 g, representing a yield per copper of 93%. Note that the product adhered to the inner wall of the flask in an amount of 0.38 g. Chemical analysis of the obtained crystals revealed that the Cu content was 31.5% (purity 99.9%) and the C content was 35.2% (purity 98.5%).

[0062] (Comparative Example 5: Solid Phase Method) A 30 ml high-speed rotary mixer was charged with 4.4 g (16.6 mmol) of copper hydroxide, 6.3 g (33.3 mmol) of trimesic acid, and 13 ml of methanol, and the mixture was stirred at 16,000 rpm (circumferential speed: 30 m / s) for 15 minutes to carry out a solid-state reaction. The solid was filtered and washed with methanol to obtain a blue solid. The resulting blue solid was dried in a tray dryer at 150 °C under vacuum for 10 hours. The dry weight was 2.16 g (40% yield). Powder X-ray analysis confirmed that the resulting crystals were HKUST-1. Chemical analysis of the resulting crystals revealed a Cu content of 42.9% (theoretical value: 31.52%) and a C content of 30.42% (theoretical value: 35.74%).

[0063] (evaluation) <Particle size> The maximum length of a representative particle from the scanning electron microscope image of the obtained HKUST-1 was taken as the particle size. When the particle size varied significantly, it was shown as a range of particle sizes.

[0064] <Specific surface area> The BET specific surface area of ​​the obtained HKUST-1 was measured using a commercially available gas adsorption apparatus (Autosorb iQ, manufactured by Anton Paar Co., Ltd.). Measurement conditions Pretreatment: 150℃ 24 hours Measurement temperature: 87K (liquid argon) Measurement gas: Argon gas

[0065] <Angle of repose> (Injection method): The powder was dropped from above, and the inclination angle of the surface layer deposited in a cone shape at the bottom was measured with a protractor. (Slope method): When the powder was tilted, the angle of inclination of the slope at the end of sliding was measured with a protractor.

[0066] <Bulk specific gravity> Using a 100 ml measuring cylinder, 20 g of powder was filled in an untapped state (loose), and the volume of the powder was measured.

[0067] [Table 1]

[0068] The above results confirmed that the rotation method had a high yield. Furthermore, the obtained metal-organic framework was non-adhesive, had a small angle of repose, a high bulk density, and was easy to handle.

[0069] Embodiments of the present disclosure include the following items. [Section 1] A method for producing a metal organic framework containing metal ions and organic ligands by a solution process, comprising: providing a solution containing metal ions and an organic compound in a container; rotating the container so that the axis of rotation is less than 90° relative to the surface of the solution; A method for producing a metal organic framework, comprising: [Section 2] Item 2. The method according to item 1, wherein the metal ions are ions of a metal selected from Zr, Zn, Mn, Cu, Co, Fe, and Al. [Section 3] Item 3. The method according to item 1 or 2, wherein the metal ion is a copper (II) ion. [Section 4] Item 4. The method according to Item 3, wherein the copper ion source is copper(II) nitrate. [Section 5] Item 5. The method according to any one of items 1 to 4, wherein the organic compound is benzenetricarboxylic acid. [Section 6] Item 6. The production method according to any one of items 1 to 5, wherein the solution further contains a base. [Section 7] Item 7. The method according to Item 6, wherein the base is N,N-diethylformamide or N,N-dimethylformamide. [Section 8] 8. The method according to any one of items 1 to 7, wherein the solution contains water, alcohol, or a mixture thereof as a solvent. [Section 9] Item 9. The method according to any one of items 1 to 8, wherein the container is an eggplant-shaped container or a round-bottomed container. [Section 10] Item 10. The manufacturing method according to any one of items 1 to 9, wherein the angle of the rotation axis relative to the liquid surface of the solution is 10° or more and 45° or less. [Section 11] Item 11. The manufacturing method according to any one of items 1 to 10, wherein the rotation speed of the container is 10 rpm or more and 300 rpm or less. [Section 12] Item 12. The method according to any one of items 1 to 11, wherein the temperature during rotation of the solution is 40°C or higher and 100°C or lower. [Section 13] The specific surface area of ​​the resulting metal-organic framework is 1,700 m 2 Item 13. The method according to any one of items 1 to 12, wherein the solubility is 1 / g or more. [Section 14] Item 14. The manufacturing method according to any one of items 1 to 13, wherein the angle of repose of the obtained metal organic framework by the injection method is 35° or less, and the angle of repose by the tilt method is 45° or less.

Claims

1. A method for producing a metal organic framework containing metal ions and organic ligands by a solution process, comprising: providing a solution containing metal ions and an organic compound in a container; rotating the container so that the axis of rotation is less than 90° relative to the surface of the solution; A method for producing a metal organic framework, comprising:

2. The method according to claim 1 , wherein the metal ions are ions of a metal selected from Zr, Zn, Mn, Cu, Co, Fe, and Al.

3. The method according to claim 1 , wherein the metal ions are copper (II) ions.

4. 4. The method of claim 3, wherein the copper ion source is copper (II) nitrate.

5. The method according to claim 1 , wherein the organic compound is benzenetricarboxylic acid.

6. The method of claim 1 , wherein the solution further comprises a base.

7. The method according to claim 6, wherein the base is N,N-diethylformamide or N,N-dimethylformamide.

8. The method according to claim 1 , wherein the solution contains water or alcohol, or a mixture thereof, as a solvent.

9. The method according to claim 1 , wherein the container is an eggplant-shaped container or a round-bottomed container.

10. The manufacturing method according to claim 1 , wherein the angle of the rotation axis with respect to the liquid surface of the solution is 10° or more and 45° or less.

11. The manufacturing method according to claim 1 , wherein the rotation speed of the container is 10 rpm or more and 300 rpm or less.

12. The method according to claim 1 , wherein the temperature of the solution during rotation is 40° C. or higher and 100° C. or lower.

13. The specific surface area of ​​the resulting metal organic framework is 1,700 m ２ The method according to claim 1, wherein the SiO2 content is 1 / g or more.

14. The method according to claim 1 , wherein the angle of repose of the obtained metal organic framework is 35° or less when measured by the injection method, and 45° or less when measured by the tilt method.

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