Method for producing metal-organic structure
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Filing Date
- 2023-07-26
- Publication Date
- 2026-07-24
Abstract
Description
Method for producing metal-organic framework
[0001] The present invention relates to a method for producing a metal organic framework (MOF).
[0002] A group of materials called metal-organic frameworks (MOFs) have been attracting attention in fields such as gas storage and gas separation. Metal-organic frameworks are compounds with a structure in which metal atoms are cross-linked by organic ligands, and are typically porous. Porous metal-organic frameworks are also known as porous coordination polymers (PCPs).
[0003] Typically, liquid-phase synthesis methods such as solution synthesis, hydrothermal synthesis, microwave synthesis, and ultrasonic synthesis are used as methods for producing metal-organic frameworks. Solid-phase synthesis methods using a mortar, ball mill, or the like are also sometimes used. Furthermore, in recent years, methods for synthesizing metal-organic frameworks using a twin-screw kneading device called an extruder have also been reported. In this method, a first reactant containing a specific metal ion donor and a second reactant containing a specific organic ligand are kneaded under pressure and shear force to synthesize a metal-organic framework (Patent Document 1).
[0004] The present applicant has disclosed a method for producing a metal-organic framework, which comprises simultaneously and continuously applying centrifugal force and shear force to a blend containing a metal ion donor, a multidentate ligand, and a solvent (Patent Document 2). This document mainly describes an embodiment in which a rotating thin film type high-speed mixer (see Non-Patent Document 1) is applied to the production of a metal-organic framework. By employing such a method, it is possible to produce a high-quality metal-organic framework in a short period of time.
[0005] U.S. Patent No. 9,815,222 WO 2020 / 230820
[0006] Haruo Shibuya, "Medialess Dispersion Machine," J. Jpn. Soc. Colour Mater., 86 [7], 265-269 (2013)
[0007] However, the present inventors have found that when the above-mentioned method is adopted, it is necessary to use an apparatus with a complicated configuration, and it may be difficult to scale up. That is, an object of the present invention is to provide a simpler method for producing a high-quality metal-organic framework.
[0008] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have discovered a new method for applying a turbine-stator type high-speed mixer to substance synthesis instead of a rotating thin film type high-speed mixer. The turbine-stator type high-speed mixer is a type of media-less disperser that has conventionally been used exclusively for dispersing and / or atomizing particles and droplets (see Non-Patent Document 1).
[0009] The present invention includes, for example, the following aspects: [1] A method for producing a metal organic framework, the method comprising: preparing an agitator having a turbine and a stator surrounding the turbine; preparing a blend containing a metal ion donor, a multidentate ligand, and a solvent; and applying a shear force generated between the turbine and the stator to the blend by rotating the turbine relative to the stator in the agitator. [2] The method according to [1], wherein the solvent is a poor solvent for at least one of the metal ion donor and the multidentate ligand. [3] The method according to [1] or [2], wherein the solvent has a Hildebrand solubility parameter of 9.0 or higher. [4] The method according to any one of [1] to [3], wherein the amount of the solvent is within a range of 25 to 2000 wt % with respect to the total amount of the metal ion donor and the multidentate ligand. [5] The method according to any one of [1] to [4], wherein the method is carried out at a temperature below the normal boiling point of the solvent. [6] The manufacturing method according to any one of [1] to [5], wherein the shortest distance between the turbine and the stator is in the range of 0.1 mm to 5 mm. [7] The manufacturing method according to any one of [1] to [6], wherein the metal-organic framework is a porous coordination polymer.
[0010] According to the present invention, it is possible to produce a high-quality metal-organic framework by a simpler method.
[0011] FIG. 1A is a perspective view showing an example of an agitator (homomixer) according to one embodiment of the present invention. FIG. 1B is a bottom view of the agitator shown in FIG. 1A. FIG. 2 is a cross-sectional view showing an example of use of the agitator shown in FIGS. 1A and 1B. FIG. 3A is an exploded perspective view showing an example of an agitator (comb-tooth turbine / stator) according to another embodiment of the present invention. FIG. 3B is a bottom perspective view showing the assembled state of the agitator shown in FIG. 3A. FIG. 4 is a cross-sectional view showing an example of use of the agitator shown in FIGS. 3A and 3B. Note that in FIG. 4, the turbine and stator portions are depicted as side views for simplicity of illustration. FIG. 5A shows an XRD (X-ray diffraction) pattern of a metal-organic framework (HKUST-1) synthesized under the conditions of Example 1. FIG. 5B shows an XRD pattern of a metal-organic framework (HKUST-1) synthesized under the conditions of Comparative Example A2. FIG. 6A shows an XRD pattern of a metal-organic framework [MOF-74(Mg)] synthesized under the conditions of Example 7. FIG. 6B shows an XRD pattern of the metal-organic framework [MOF-74(Mg)] synthesized under the conditions of Comparative Example A4. FIG. 7A shows an XRD pattern of the metal-organic framework (ZIF-8) synthesized under the conditions of Example 12. FIG. 7B shows an XRD pattern of the metal-organic framework (ZIF-8) synthesized under the conditions of Comparative Example A13. FIG. 8A shows an XRD pattern of the metal-organic framework (ZIF-67) synthesized under the conditions of Example 26. FIG. 8B shows an XRD pattern of the metal-organic framework (ZIF-67) synthesized under the conditions of Comparative Example A32.
[0012] A manufacturing method according to one embodiment of the present invention will be described below. When referring to the drawings, components that perform the same or similar functions are designated by the same reference numerals, and redundant explanations will be omitted.
[0013] A method for producing a metal-organic framework according to one embodiment of the present invention includes: preparing a mixer including a turbine and a stator surrounding the turbine; preparing a blend containing a metal ion donor, a multidentate ligand, and a solvent; and applying a shear force generated between the turbine and the stator to the blend by rotating the turbine relative to the stator in the mixer. This production method may also include adding a separately prepared blend to a reaction vessel. Alternatively, this production method may include forming the blend inside the reaction vessel by sequentially adding components of the blend to the reaction vessel.
[0014] The agitator may be a high-speed agitator known as a turbine / stator agitator. This agitator includes a turbine and a stator surrounding the turbine. The turbine rotates relative to the stator. This allows the mixture of reactants to be subjected to a strong shear force generated between the turbine and the stator.
[0015] As the turbine / stator type agitator, for example, a homo mixer or a comb-tooth turbine / stator can be used. The agitator may be an in-line disperser or a combined agitator including a turbine / stator type agitator. The use of these agitators as conventional media-less dispersers is described in detail, for example, in Non-Patent Document 1. Configuration examples of the homo mixer and comb-tooth turbine / stator will be described below with reference to the drawings.
[0016] Fig. 1A is a perspective view showing an example of an agitator according to one embodiment of the present invention. Fig. 1B is a bottom view of the agitator shown in Fig. 1A. The agitator 100A shown in Fig. 1A and Fig. 1B is a homogenizer and includes a turbine 10A and a stator 20A surrounding the turbine 10A. In the agitator 100A, the turbine 10A is configured to be rotatable relative to the stator 20A.
[0017] FIG. 2 is a cross-sectional view showing an example of use of the agitator shown in FIGS. 1A and 1B. The reaction apparatus 1A shown in FIG. 2 includes an agitator 100A and a reaction vessel 200. The agitator 100A includes a turbine 10A and a stator 20A. The turbine 10A and the stator 20A are optionally connected to a shaft 30A via a bearing 40A. A deflector plate 50A is optionally installed above the shaft 30A. The reaction apparatus 1A can have the same configuration as when the agitator 100A is used as a media-less disperser, except that the contents of the formulation F, which will be described later, are different.
[0018] The turbine 10A, stator 20A, shaft 30A, and diverter plate 50A are typically made of an alloy such as stainless steel. The bearing 40A may be made of, for example, a plastic such as Teflon (registered trademark), or an alloy such as stainless steel. In the former case, replacement is easy when worn. In the latter case, the possibility of contamination of the reaction system can be reduced.
[0019] When producing a metal-organic framework using the reaction apparatus 1A, first, a formulation F is introduced into the reaction vessel 200. Next, in the agitator 100A, the turbine 10A is rotated at high speed relative to the stator 20A. As a result, as exemplarily depicted by the hollow arrows in FIG. 2 , the formulation F is sucked in from the bottom of the stator 20A, ejected upward, collides with the flow-direction plate 50A, and circulates within the reaction vessel 200. At this time, a strong shear force is applied to the formulation F between the turbine 10A and the stator 20A. By applying such a shear force, a desired metal-organic framework can be synthesized from the formulation F.
[0020] Fig. 3A is an exploded perspective view showing an example of an agitator according to another embodiment of the present invention. Fig. 3B is a bottom perspective view showing the agitator shown in Fig. 3A in an assembled state. The agitator 100B shown in Figs. 3A and 3B is a comb-tooth turbine stator and includes a turbine 10B and a stator 20B surrounding the turbine 10B. In the agitator 100B, the turbine 10B is configured to be rotatable relative to the stator 20B.
[0021] FIG. 4 is a cross-sectional view (partial side view) showing an example of use of the agitator shown in FIGS. 3A and 3B. The reactor 1B shown in FIG. 4 includes an agitator 100B and a reaction vessel 200. The agitator 100B includes a turbine 10B (not shown) and a stator 20B. The turbine 10B and the stator 20B are optionally connected to a shaft 30B via a bearing 40B. The reactor 1B can have the same configuration as when the agitator 100B is used as a media-less disperser, except that the contents of the formulation F described below are different. The materials of the turbine 10B, stator 20B, shaft 30B, and bearing 40B can be, for example, the same as those described above for the turbine 10A, stator 20A, shaft 30A, and bearing 40A.
[0022] When producing a metal-organic framework using the reaction apparatus 1B, first, a compound F is introduced into the reaction vessel 200. Next, in the agitator 100B, the turbine 10B is rotated at high speed relative to the stator 20B. As a result, as exemplarily depicted by the hollow arrows in FIG. 4 , the compound F is sucked from above and below the stator 20B, ejected laterally from the comb-tooth slits, collides with the wall surface of the reaction vessel 200, and circulates within the reaction vessel 200. At this time, a strong shear force is applied to the compound F between the turbine 10B and the stator 20B. By applying such a shear force, a desired metal-organic framework can be synthesized from the compound F.
[0023] The present inventors have found that the use of the turbine / stator type agitator as described above allows for the production of metal organic frameworks of higher quality than when using high-speed agitating blades such as a disk turbine and a disperser, or a regular stirrer. This difference is presumably due mainly to the large shear force generated between the turbine and the stator.
[0024] Furthermore, the present inventors have also found that the use of the above-mentioned agitator facilitates scale-up compared to, for example, the use of a high-speed agitator blade or stirrer. When a high-speed agitator blade or stirrer is used, scaling up (i.e., increasing the size of the reaction vessel) increases the distance between the vessel and the agitator blade or stirrer. This makes it difficult to apply shear force to the reactants, resulting in a decrease in the amount and / or quality of the resulting metal-organic framework. In contrast, when the above-mentioned agitator is used, the distance between the turbine and the stator (described later as "clearance") does not change even when scaling up is performed. Therefore, when the above-mentioned agitator is used, it becomes possible to produce a high-quality metal-organic framework with a high yield, even when scaling up is performed.
[0025] Furthermore, as disclosed in Patent Document 2, when a rotating thin film type high-speed agitator is used, it is possible to synthesize a high-quality metal-organic framework in a short reaction time. However, this agitator has a complex structure and is not very versatile. In particular, this agitator generates shear force mainly by contacting the reactants with the inner wall of the reaction vessel using centrifugal force from the rotating blades. Therefore, when attempting to scale up using this device, it is necessary to increase the size of the reaction vessel and the size of the rotating blades accordingly. Therefore, when using this agitator, it is difficult to scale up the synthesis simply by increasing the size of the reaction vessel. In contrast, when using the above-mentioned turbine / stator type agitator, scale up can be easily achieved by applying the same agitator to a larger reaction vessel.
[0026] Patent Document 2 also describes an embodiment in which a rotating thin film type high-speed agitator is used in a continuous manner. In this case, scale-up is easier than when this agitator is used in a batchwise manner. However, when the reaction is carried out in a continuous manner, the viscosity of Blend F needs to be sufficiently low. That is, in this case, the amount of solvent in Blend F needs to be increased. In contrast, in the embodiment of the present invention in which a turbine / stator type agitator is used, there is no such limitation. By keeping the amount of solvent low, it is possible to reduce the production cost of the metal-organic framework and the environmental load caused by the synthesis.
[0027] In the turbine / stator type agitator, the shortest distance (clearance) between the turbine and the stator is, for example, in the range of 0.1 mm to 5 mm, and preferably in the range of 0.3 mm to 1.5 mm. If the clearance is too small, the reactants are likely to get stuck between the turbine and the stator. If the clearance is too large, the shear force applied to the reactants is small, making it difficult to synthesize the metal-organic framework.
[0028] Usable turbine / stator agitators include, for example, those shown in Table 1 below. These turbine / stator agitators are commercially available for use in dispersing and / or atomizing particles and droplets. Note that these are merely examples, and other agitators including a turbine and a stator may also be used.
[0029]
[0030] There is no particular limitation on the type of metal-organic framework to be produced. A metal-organic framework having a desired structure can be produced by appropriately combining the type and coordination number of metal ions with the type and topology of multidentate ligands. The metal-organic framework may contain two or more types of metal elements, or may contain two or more types of multidentate ligands. The metal-organic framework may further contain a monodentate ligand. The metal-organic framework may be porous. That is, the metal-organic framework may be a porous coordination polymer.
[0031] Specific examples of metal-organic frameworks include those described in the following documents: Document 1: Yabing He et al., Methane Storage in Metal-Organic Frameworks, Chem Soc Rev, 2014 Document 2: Jarad A. Mason et al., Evaluating metal-organic frameworks for natural gas storage, Chem. Sci., 2014, 5, 32-51 Document 3: International Publication No. 2019 / 026872
[0032] As described above, the compound used as the raw material for the metal-organic framework contains a metal ion donor, a multidentate ligand, and a solvent. Any substances can be used as the metal ion donor and the multidentate ligand as long as they are suitable as a combination for synthesizing a metal-organic framework.
[0033] Examples of the metal element constituting the metal ion donor include any element belonging to alkali metals (Group 1), alkaline earth metals (Group 2), and transition metals (Groups 3 to 12). The metal element is typically selected from the group consisting of magnesium, calcium, iron, aluminum, zinc, copper, nickel, cobalt, zirconium, and chromium. The metal ion donor may contain multiple metal elements. Alternatively, multiple metal ion donors containing different metal elements may be used in combination.
[0034] Typically, a metal salt is used as the metal ion donor. The metal ion donor may be an organic salt or an inorganic salt. The metal ion donor is typically selected from the group consisting of hydroxide salts, carbonate salts, acetate salts, sulfate salts, nitrate salts, and chloride salts. Multiple metal ion donors containing the same metal element may be used in combination. The metal ion donor may be in the form of a so-called secondary building unit (SBU). As such a secondary building unit, any one used in the synthesis of known metal-organic frameworks may be selected.
[0035] The polydentate ligand is typically an organic polydentate ligand, and is selected from the group consisting of, for example, a carboxylate anion, an amine compound, a sulfonate anion, a phosphate anion, and a heterocyclic compound. Examples of the carboxylate anion include a dicarboxylic acid or tricarboxylic acid anion. Specific examples include anions of citric acid, malic acid, terephthalic acid, isophthalic acid, trimesic acid, and derivatives thereof. Examples of the heterocyclic compound include bipyridine, imidazole, adenine, and derivatives thereof. Multiple polydentate ligands may be used.
[0036] The type of solvent contained in the formulation is not particularly limited, and solvents commonly used in the synthesis of metal-organic frameworks can be used. However, it is preferable that the solvent be a poor solvent for at least one of the metal ion donor and the multidentate ligand. When such a configuration is adopted, the formulation does not become a complete solution, but rather becomes a semi-solid state with solids remaining, typically a slurry. This allows for more effective application of shear force to the formulation. Here, a solvent being a "poor solvent" for a certain target refers to a solvent whose solubility in the target in the solvent is 1 g / 50 mL (= 20 g / L) or less at 25°C and atmospheric pressure. Examples of usable solvents include water; alcohols such as methanol, ethanol, and isopropyl alcohol; carboxylic acids such as formic acid and acetic acid; amides such as N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF); and esters such as ethyl acetate. A mixture of multiple solvents may also be used.
[0037] It is particularly preferable that the solvent has a Hildebrand solubility parameter of 9.0 or more. In this case, it is possible to synthesize a metal organic framework of higher quality. Table 2 shows examples of Hildebrand solubility parameters of representative solvents. When a mixed solvent is used, the Hildebrand solubility parameter is a weighted average value according to the mixing ratio. As shown in Table 2, specific examples of solvents having a Hildebrand solubility parameter of 9.0 or more include tetrahydrofuran, chloroform, acetone, methylene chloride, ethylene dichloride, dioxane, isopropyl alcohol, ethanol, dimethylformamide, acetonitrile, acetic acid, dimethyl sulfoxide, methanol, ethylene glycol, and water.
[0038]
[0039] The amount of the solvent is, for example, in the range of 25 to 2000 wt %, preferably in the range of 25 to 1000 wt %, relative to the total amount of the metal ion donor and the multidentate ligand. Adoption of such a configuration can, for example, improve the production efficiency of the metal-organic framework. Generally, in embodiments of the present invention using a turbine / stator-type agitator, it is possible to lower the amount of solvent (i.e., increase the concentration of the blend) compared to when a rotating thin film-type high-speed agitator is used. For example, in some embodiments of the present invention, a high-quality metal-organic framework can be synthesized even when the amount of solvent is 100 wt % or less (e.g., 25 to 100 wt %). By keeping the amount of solvent low, it is possible to reduce the production cost of the metal-organic framework and the environmental impact of the synthesis.
[0040] The above-mentioned formulation may further contain an additional substance such as a reaction accelerator. The reaction accelerator is, for example, a basic substance or an acidic substance, and is typically a basic substance. Examples of basic substances include diethylamine, triethylamine, 2,6-lutidine, pyridine, imidazole, potassium hydroxide, and sodium hydroxide. Examples of acidic substances include formic acid, acetic acid, trifluoroacetic acid, sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. As the additional substance, multiple reaction accelerators may be used in combination. As the additional substance, a reaction inhibitor may be added.
[0041] The above production is preferably carried out while controlling the reaction temperature. In this case, the above mixing is preferably carried out at a temperature below the normal boiling point of the solvent. The above mixing is carried out at a temperature of, for example, 80°C or lower, preferably 60°C or lower. In this way, it is possible to produce the metal organic framework while an appropriate amount of the solvent remains in the blend.
[0042] In the above production, the rotation speed of the agitator (i.e., the rotation speed of the turbine) is, for example, 1,000 to 20,000 rpm, preferably 5,000 to 15,000 rpm. The rotation speed can be adjusted appropriately depending on the concentration of the blend, etc. If the rotation speed is too low, the shear force applied to the blend as a reactant may be insufficient. If the rotation speed is too high, it may become difficult to control the temperature of the reaction system.
[0043] The following demonstration experiment was carried out to compare the use of a turbine / stator type high-speed agitator with the use of a non-turbine / stator type high-speed agitator.
[0044] Examples 1 to 30: Turbine / stator-type high-speed mixer A metal ion donor, a multidentate ligand, a solvent, and optionally a reaction accelerator shown in Table 3 were placed in a batch-type reaction vessel. Next, high-speed mixing was carried out using a turbine / stator-type high-speed mixer (Homomixer MARK II 2.5 type: manufactured by Primix Corporation, or Neokaiser (registered trademark): manufactured by Primix Corporation) under the reaction conditions shown in Table 3. This resulted in a metal-organic framework being obtained. Note that Neokaiser is a type of comb-tooth turbine-stator described with reference to FIG. 4.
[0045] Comparative Examples A1 to A33: High-speed stirring blade or stirrer A metal ion donor, a multidentate ligand, a solvent, and optionally a reaction accelerator shown in Table 4 were placed in a batch reaction vessel. Next, high-speed stirring was carried out under the reaction conditions shown in Table 4 using a high-speed stirring blade (Homodisper, manufactured by Primix Corporation) or a commercially available stirrer.
[0046] Comparative Examples B1 to B39: Rotating Thin Film Type High-Speed Stirrer The metal ion donor, multidentate ligand, solvent, and optionally, reaction accelerator shown in Table 5 were added to a rotating thin film type high-speed stirrer (Filmix (registered trademark) 56-L model; manufactured by Primix Corporation). Next, high-speed stirring was carried out under the reaction conditions shown in Table 5.
[0047] Evaluation The samples obtained by each of the above methods were dried under reduced pressure at room temperature for 24 hours using a vacuum desiccator (MVD-300; manufactured by AS ONE Corporation). The dried samples were subjected to XRD (X-ray diffraction) measurement using an X-ray diffractometer (MiniFlex; manufactured by Rigaku Corporation). Furthermore, at least some of the samples were heated and vacuum dried at 140°C for 4 hours using a gas adsorption pretreatment device (BELPREP-vacIII; manufactured by Microtrac-Bel), and then the BET specific surface area (N ２ ;77K) was measured.
[0048] The presence or absence of crystalline peaks in XRD measurement and the BET specific surface area S ＢＥＴ The quality of the obtained metal organic framework was evaluated based on the size of the particle. These results are shown in Tables 3 to 5.
[0049] The following abbreviations are used in Tables 3 to 5: BTC: 1,3,5-benzenetricarboxylic acid (trimesic acid), 2,5-DHTP: dihydroxyterephthalic acid, 2-Mim or Mim: 2-methylimidazole, 1,3-BDC or iBDC: isophthalic acid, DOBPDC: 4,4'-dioxidobiphenyl-3,3'-dicarboxylic acid, Im: imidazole, BIm: benzimidazole, 1,4-BDC or pBDC: terephthalic acid, IPA: isopropyl alcohol, AcOH: acetic acid, TEA: triethylamine, DEA: diethanolamine, INA: 4-pyridinecarboxylic acid, ADC: acetylenedicarboxylic acid, DOT: dihydroxyterephthalic acid, BTC3Na: trisodium 1,3,5-benzenetricarboxylate
[0050]
[0051]
[0052]
[0053] A comparison of Table 3 with Table 4 shows that by using a turbine / stator type high-speed stirrer, a metal organic framework of higher quality can be synthesized while significantly shortening the reaction time compared to when a high-speed stirring blade or stirrer is used. Furthermore, a comparison of Table 3 with Table 5 shows that by using a turbine / stator type high-speed stirrer, a metal organic framework of equal or higher quality can be synthesized on a larger scale compared to when a swirling thin film type high-speed stirrer is used.
[0054] FIG. 5A shows the XRD pattern of the metal-organic framework (HKUST-1) synthesized under the conditions of Example 1. FIG. 5B shows the XRD pattern of the metal-organic framework (HKUST-1) synthesized under the conditions of Comparative Example A2. As can be seen from comparing the two, the peaks (indicated by two arrows) of the raw material copper (II) hydroxide remain in FIG. 5B. This result shows that when a homomixer is used, a higher quality metal-organic framework (HKUST-1) is obtained compared to when a stirrer is used. This difference is also reflected in the difference in BET specific surface area.
[0055] Figure 6A shows the XRD pattern of the metal-organic framework [MOF-74(Mg)] synthesized under the conditions of Example 7. Figure 6B shows the XRD pattern of the metal-organic framework [MOF-74(Mg)] synthesized under the conditions of Comparative Example A4. As can be seen from the comparison of the two, when synthesis is performed on a large scale (approximately 2 kg as the weight of the metal ion donor), a high-quality metal-organic framework is obtained under the former conditions, whereas a metal-organic framework is not successfully synthesized under the latter conditions. This difference is also reflected in the difference in BET specific surface area.
[0056] FIG. 7A shows the XRD pattern of the metal-organic framework (ZIF-8) synthesized under the conditions of Example 12. FIG. 7B shows the XRD pattern of the metal-organic framework (ZIF-8) synthesized under the conditions of Comparative Example A13. As can be seen from the comparison between the two, peaks of zinc oxide (indicated by three arrows) that are the raw material remain in FIG. 7B. This result shows that when the homomixer is used, a higher quality metal-organic framework (ZIF-8) is obtained compared to when the stirrer is used. This difference is also reflected in the difference in BET specific surface area.
[0057] FIG. 8A shows the XRD pattern of the metal-organic framework (ZIF-67) synthesized under the conditions of Example 26. FIG. 8B shows the XRD pattern of the metal-organic framework (ZIF-67) synthesized under the conditions of Comparative Example A32. As can be seen from the comparison between the two, in FIG. 8B, the peak of the raw material cobalt (II) hydroxide (indicated by a single arrow) remains. This result shows that when the homomixer is used, a higher quality metal-organic framework (ZIF-67) is obtained compared to when the homodisper is used. This difference is also reflected in the difference in BET specific surface area.
[0058] As described above, it was found that for a wide variety of metal-organic frameworks, by using a turbine / stator-type high-speed stirrer, it is possible to synthesize metal-organic frameworks of higher quality while significantly shortening the reaction time compared to when a high-speed stirring blade or stirrer is used. Similarly, it was found that for a wide variety of metal-organic frameworks, by using a turbine / stator-type high-speed stirrer, it is possible to synthesize metal-organic frameworks of equal or higher quality on a larger scale compared to when a spinning thin film-type high-speed stirrer is used.
Claims
1. To prepare a stirrer comprising a turbine and a stator surrounding the turbine; To prepare a compound containing a metal ion donor, a polydentate ligand, and a solvent; Introducing the formulation into a reaction vessel larger than the aforementioned stirrer; In the aforementioned agitator, the turbine is rotated relative to the stator to apply a shear force generated between the turbine and the stator to the mixture; A method for producing a metal-organic structure containing [the specified element].
2. The manufacturing method according to claim 1, wherein the solvent is a poor solvent for at least one of the metal ion donor and the polydentate ligand.
3. The manufacturing method according to claim 1 or 2, wherein the solvent has a Hildebrand solubility parameter of 9.0 or higher.
4. The manufacturing method according to claim 1 or 2, wherein the amount of the solvent is in the range of 25 to 2000% by weight relative to the total amount of the metal ion donor and the polydentate ligand.
5. The manufacturing method according to claim 1 or 2, wherein the method is carried out at a temperature below the normal boiling point of the solvent.
6. The manufacturing method according to claim 1 or 2, wherein the shortest distance between the turbine and the stator is in the range of 0.1 mm to 5 mm.
7. The manufacturing method according to claim 1 or 2, wherein the metal-organic structure is a porous coordination polymer.