Method for preparing metal organic framework

Abstract

[Problem] To provide a simple method for producing a high-quality metal organic framework. [Solution] A method for producing a high-quality metal-organic framework according to the present invention comprises: providing a stirrer having a turbine and a stator surrounding the turbine; providing a formulation comprising a metal ion donor, a polydentate ligand, and a solvent; and rotating a turbine in the agitator relative to the stator and generating a shear force therebetween to apply to the formulation.

Description

Technical Field

[0001] The invention relates to a method for preparing Metal-Organic Frameworks (MOF). Background Art

[0002] Metal-organic frameworks (MOFs) have attracted much attention in the fields of gas storage and gas separation. Compounds with a structure formed by metal atoms cross-linked by organic ligands are usually porous and are therefore also called porous coordination polymers (PCPs).

[0003] Common methods for preparing metal-organic frameworks include liquid phase synthesis methods, such as solution method, hydrothermal method, microwave method and ultrasonic method. In addition, there are also solid phase synthesis methods using mortar, ball mill, etc.; recently, there is also a method of synthesizing metal-organic frameworks using a biaxial mixing device (such as an extruder), by mixing a first reactant having a specific metal ion donor and a second reactant containing a specific organic ligand under a continuous pressure and shear force environment to complete the preparation of the metal-organic framework (Patent Document 1).

[0004] The applicant has previously disclosed a method for preparing a metal organic framework, comprising simultaneously and continuously applying centrifugal force and shear force to a composition comprising a metal ion donor, a multidentate ligand and a solvent (Patent Document 2), wherein in one embodiment, the metal organic framework is prepared by a cyclonic thin film type high-speed mixer (see Non-Patent Document 1). The present invention provides a method capable of producing a high-quality metal organic framework in a short time. Citation list Patent Literature

[0005] [Patent Document 1] US 9,815,222 B2 [Patent Document 2] WO2019 / 026872 Non-patent literature

[0006] [Non-patent document 1] Haruo Shibuya, “Media-less Dispersion Machines”, J. Jpn. Soc. Colour Mater., 86[7], 265-269 (2013) Summary of the invention Technical issues

[0007] However, the present applicant has found that when the above method is used, a device with a complex structure is required and it is difficult to carry out large-scale production. Therefore, the purpose of the present invention is to provide a method for preparing a high-quality metal organic framework in a short time. Solution

[0008] In order to solve the above problems, the inventors conducted in-depth research and found that a turbine-stator high-speed agitator can be used to replace a vortex film high-speed agitator to prepare metal organic frameworks. The turbine-stator high-speed agitator is a dispersion device that does not require a medium and is mainly used to disperse and / or atomize particles and droplets (see non-patent document 1).

[0009] Some aspects of the present invention are as follows: [1] A method for preparing a metal organic framework, comprising: providing a stirrer equipped with a turbine and a stator surrounding the turbine; providing a formulation comprising a metal ion donor, a multidentate ligand and a solvent; and rotating the turbine relative to the stator in the stirrer to generate a shear force between the turbine and the stator and apply the shear force to the formulation. [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 greater than or equal to 9.0. [4] The method according to any one of [1] to [3], wherein the amount of the solvent used is in the range of 30% to 2000% by weight of 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 lower than the normal boiling point of the solvent. [6] A 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 method according to any one of [1] to [6], wherein the metal organic framework is a porous coordination polymer. Beneficial effects of the present invention

[0010] The present invention prepares high-quality metal organic frameworks through a simpler method. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1A A perspective view showing an agitator (homogenizer) according to one embodiment of the present invention. Figure 1Bfor Figure 1A Bottom view of the agitator shown. Figure 2 Display as Figure 1A and Figure 1B An exemplary cross-sectional view of the agitator is shown in operation. Figure 3A An exploded perspective view showing an agitator (comb-tooth type turbine stator) according to another embodiment of the present invention. Figure 3B show Figure 3A The stirrer is shown in a bottom perspective view when assembled. Figure 4 Display usage Figure 3A and Figure 3B A cross-sectional view of an embodiment of the agitator shown in Figure 4 In the figure, the turbine and stator parts are presented in the form of side views to simplify the description. Figure 5A The X-ray diffraction pattern of the metal organic framework (HKUST-1) synthesized in Example 1 is shown. Figure 5B The X-ray diffraction pattern of the metal organic framework (HKUST-1) synthesized in Comparative Example A2 is shown. Fig. 6A The X-ray diffraction pattern of the metal organic framework [MOF-74(Mg)] synthesized in Example 7 is shown. Figure 6B The X-ray diffraction pattern of the metal organic framework [MOF-74(Mg)] synthesized in Comparative Example A4 is shown. Fig. 7A The X-ray diffraction pattern of the metal organic framework (ZIF-8) synthesized in Example 12 is shown. Figure 7B The X-ray diffraction pattern of the metal organic framework (ZIF-8) synthesized in Comparative Example A13 is shown. Fig. 8A The X-ray diffraction pattern of the metal organic framework (ZIF-67) synthesized in Example 26 is shown. Figure 8B The X-ray diffraction pattern of the metal organic framework (ZIF-67) synthesized in Comparative Example A32 is shown. DETAILED DESCRIPTION

[0012] Hereinafter, a preparation method according to an embodiment of the present invention will be described. When referring to the drawings, components having the same or similar functions will be marked with the same reference numerals, and repeated description will be omitted.

[0013] According to one embodiment of the present invention, a method for preparing a metal organic framework comprises the following steps: providing an agitator having a turbine and a stator surrounding the turbine; providing a formula comprising a metal ion donor, a multidentate ligand and a solvent; and rotating the turbine relative to the stator in the agitator to generate a shear force between the turbine and the stator and apply the shear force to the formula. The method may include adding a previously prepared formula to a reaction container; or, the method may also include adding each component of the formula to the reaction container in sequence and forming the formula in the container.

[0014] The agitator can be a high-speed agitator, i.e. a turbine / stator type agitator, wherein the agitator comprises a turbine and a stator surrounding the turbine. In addition, in this agitator, the turbine is configured to rotate relative to the stator. This enables a stronger shear force generated between the turbine and the stator to be applied to the formulation as a reactant.

[0015] The turbine / stator type agitator may include, for example, a homogenizer or a comb-tooth type turbine stator. The above-mentioned agitator may also be an in-line disperser or a hybrid agitator having a turbine / stator type agitator, wherein the related use methods of these conventional non-medium dispersers as agitators can be found in Non-Patent Document 1. Hereinafter, the structural examples of the homogenizer and the comb-tooth type turbine stator will be further described in conjunction with the accompanying drawings.

[0016] Figure 1A A perspective view of a stirrer according to an embodiment of the present invention is exemplarily illustrated. Figure 1B yes Figure 1A Bottom view of the blender in FIG. Figure 1A and 1B The agitator 100A shown in FIG. 1 is a homogenizing mixer, which includes a turbine 10A and a stator 20A surrounding the turbine 10A. It should be noted that in the agitator 100A, the turbine 10A is rotatable relative to the stator 20A.

[0017] Figure 2 As an example, Figure 1A and 1B A cross-sectional view of the agitator is shown in operation. Figure 2 The reaction device 1A shown includes an agitator 100A and a reaction vessel 200, wherein the agitator 100A includes a turbine 10A and a stator 20A, and the turbine 10A and the stator 20A can be connected to the shaft 30A through a bearing 40A, and in addition, a guide plate 50A can be optionally installed above the shaft 30A; in general, the configuration of the reaction device 1A can be the same as the configuration of the agitator 100A as a medium-free disperser, but in the formulation F part, it may be different (to be described later).

[0018] The turbine 10A, stator 20A, shaft 30A and guide plate 50A are usually made of alloys such as stainless steel, while the bearing 40A can be made of plastic material (e.g., Teflon) or alloys such as stainless steel. Among them, the bearing 40A made of plastic material is easier to replace when worn, while the bearing 40A made of alloys such as stainless steel can reduce the possibility of contamination of the reaction system.

[0019] When preparing a metal organic framework in a reaction device 1A, first, a formulation F is added to a reaction container 200; then, the turbine 10A in the agitator 100A is rotated at a high speed relative to the stator 20A, thereby sucking the formulation F (such as Figure 2 The solid phase is formed by the turbine 10A and the stator 20A (as shown by the hollow arrow) and ejected upward, so that it collides with the guide plate 50A and circulates in the reaction vessel 200. At this time, the strong shear force between the turbine 10A and the stator 20A can act on the formula F. By applying this shear force, the formula F can be synthesized into a metal organic framework.

[0020] Figure 3A is an exploded perspective view of a stirrer according to another embodiment of the present invention, and Figure 3B Then Figure 3A The bottom perspective view of the assembled agitator is shown. Figure 3A and 3B The illustrated agitator 100B is a comb-tooth type turbine stator, which includes a turbine 10B and a stator 20B surrounding the turbine 10B. The turbine 10B in the agitator 100B is rotatable relative to the stator 20B.

[0021] Figure 4 To show Figure 3A and 3B A cross-sectional view (partially a side view) of the agitator in operation is shown. Figure 4 The reaction device 1B shown includes an agitator 100B and a reaction vessel 200, wherein the agitator 100B includes a turbine 10B (not shown) and a stator 20B, and the turbine 10B and the stator 20B can be selectively connected to the shaft 30B through a bearing 40B. It is worth noting that the configuration of the reaction device 1B can be the same as the configuration of the agitator 100B as a medium-free disperser, but in the formulation F part, it may be different (to be described later), and the materials of the turbine 10B, the stator 20B, the shaft 30B and the bearing 40B can be the same as the materials used for the turbine 10A, the stator 20A, the shaft 30A and the bearing 40A.

[0022] When the metal organic framework is produced using the reaction device 1B, first, the formula F is added to the reaction container 200; then, the turbine 10B in the stirrer 100B is rotated at a high speed relative to the stator 20B, thereby sucking the formula F from the upper and lower parts of the stator 20B (such as Figure 4 The solid phase of the reaction vessel 200 is shown in the hollow arrow, and is ejected laterally through the comb-shaped gap. After colliding with the inner wall of the reaction vessel 200, it circulates in the vessel. At this time, the strong shear force between the turbine 10B and the stator 20B can act on the formula F. By applying this shear force, the formula F can be synthesized into a metal organic framework.

[0023] Compared with high-speed stirring blades or conventional stirrers such as disk turbines or dispersers, the use of a turbine / stator type stirrer in the present invention can produce a higher quality metal organic framework. This difference can be mainly attributed to the strong shear force generated between the turbine and the stator.

[0024] In addition, compared to the use of high-speed stirring blades or agitators, the present invention is easier to mass produce by using the above-mentioned agitator for preparation. Because when using a high-speed stirring blade or agitator, as the size of the reaction vessel increases (i.e., scale-up), the distance between the stirring blade or agitator and the container wall will increase, making it difficult to apply shear force to the reactants, resulting in a decrease in the yield and / or quality of the prepared metal organic framework. In contrast, when using the above-mentioned agitator of the present invention, even if the scale is enlarged by ten, the distance between the turbine and the stator (hereinafter referred to as "gap") will not change. Therefore, in the present invention, by using the above-mentioned agitator, high-quality metal organic frameworks can be efficiently produced even when the scale is enlarged.

[0025] In addition, as described in Patent Document 2, when a swirl film type high-speed agitator is used, a high-quality metal organic framework can be synthesized in a shorter reaction time. However, the agitator has a complex structure and poor versatility. In particular, in such an agitator, the centrifugal force generated when the blades are rotated causes the reactants to contact the inner wall of the reaction vessel to generate shear force. Therefore, when such a device is used for scale-up preparation, in addition to increasing the size of the reaction vessel, the size of the rotor blades must be increased accordingly. In other words, when such an agitator is used, it is difficult to achieve a scale-up synthesis method by simply increasing the size of the reaction vessel. In contrast, in the present invention, when the turbine / stator type agitator is used, the same agitator can be applied to a larger reaction vessel to achieve scale-up.

[0026] More specifically, Patent Document 2 also describes a continuous operation mode using a swirl film type high-speed agitator, which is easier to scale up than a batch system; however, if the reaction is carried out in a continuous mode, the viscosity of Formulation F must be quite low, that is, the amount of solvent in Formulation F must be increased. In the embodiment of the turbine / stator type agitator of the present invention, there is no such limitation or requirement, so by comparison, the amount of solvent used can be reduced, which can not only reduce the production cost of the metal organic framework, but also reduce the impact of the synthesis process on the environment.

[0027] In some embodiments of the present invention, in the turbine / stator type agitator, the shortest distance (gap) between the turbine and the stator is 0.1 mm to 5 mm, preferably 0.3 mm to 1.5 mm. If the gap is too small, the reactants are easily stuck between the turbine and the stator; but if the gap is too large, the shear force on the reactants will be reduced, increasing the difficulty of synthesizing the metal organic framework.

[0028] In some embodiments, examples of turbine / stator type agitators that can be used include the agitators shown in Table 1 below. These turbine / stator type agitators are commercially available devices designed to disperse and / or atomize particles and droplets. It should be noted that these are only used as examples, and any agitator that includes a turbine and a stator is applicable, so other devices can also be used.

[0029] Table 1

[0030] The method provided by the present invention is applicable to the preparation of various types of metal organic frameworks. Metal organic frameworks with specific structures can be obtained by appropriately selecting the type and coordination number of metal ions, as well as the type and topological structure of multidentate ligands. In some embodiments, the metal organic framework may include two or more metal elements, and may also include two or more multidentate ligands; in addition, the metal organic framework may also include monodentate ligands. The metal organic framework may be a porous structure; that is, the metal organic framework may be a porous coordination polymer.

[0031] Specific examples of metal organic frameworks include those shown in the following literature: Reference 1: Yabing He et al., Methane Storage in Metal-Organic Frameworks, Chem Soc Rev, 2014. Reference 2: Jarad A. Mason et al., Evaluating Metal-Organic Frameworks for Natural Gas Storage, Chem. Sci., 2014, 5, 32-51. Reference 3: WO2019 / 026872.

[0032] As mentioned above, the raw material formula of the metal organic framework includes a metal ion donor, a multidentate ligand and a solvent. The metal ion donor and the multidentate ligand used can be selected from any substance as long as they are a combination suitable for synthesizing the metal organic framework.

[0033] The metal element of the metal ion donor can be selected from any element of alkali metal (Group 1), alkaline earth metal (Group 2) or transition metal (Groups 3 to 12); the metal element is usually selected from magnesium, calcium, iron, aluminum, zinc, copper, nickel, cobalt, zirconium or chromium. The metal ion donor can contain multiple metal elements; in addition, multiple metal ion donors containing different metal elements can also be used in combination.

[0034] The metal ion donor is usually a metal salt, wherein the metal ion donor can be an organic salt or an inorganic salt. In some embodiments, the metal ion donor can be selected from hydroxides, carbonates, acetates, sulfates, nitrates or chlorides, and multiple metal ion donors containing the same metal element can be used in combination. In addition, the metal ion donor can be a secondary building block, wherein the secondary building block can be selected from any known unit suitable for synthesizing a metal organic framework.

[0035] Generally speaking, the multidentate ligand is an organic multidentate ligand, which can be selected from carboxylic acid anions, amine compounds, sulfonic acid anions, phosphate anions or heterocyclic compounds. It is worth noting that the carboxylic acid anions can also include dicarboxylic acid anions and tricarboxylic acid anions. Specific implementation examples include anions of citric acid, malic acid, terephthalic acid, isophthalic acid, trimerized benzoic acid, etc. and their derivatives, while heterocyclic compounds can include bipyridine, imidazole, adenine and its derivatives. Therefore, a variety of multidentate ligands are applicable.

[0036] There is no particular limitation on the type of solvent in the above formulation, and various solvents suitable for synthesizing metal ion donors can be used; in some embodiments, it is preferred that the solvent used is a "poor solvent" for at least one of the metal ion donor and the multidentate ligand, whereby the formulation will not be a complete solution, but will present a semi-solid state, usually a slurry containing residual solids, so that shear force can be more effectively applied to the above formulation. The term "poor solvent" used herein refers to a solvent in which the solubility of a substance at 25°C and atmospheric pressure is 1g / 50mL (i.e., 20g / L) or less. Among them, in some embodiments, the solvent may include water, alcohols (such as methanol, ethanol and isopropanol), 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), and also a mixture of multiple solvents.

[0037] Preferably, the Hildebrand solubility parameter of the above solvent is 9.0 or higher, thereby synthesizing a higher quality metal organic framework. Table 2 shows the Hildebrand solubility parameters of various solvents as examples, wherein when a mixed solvent is used, its Hildebrand solubility parameter is a weighted average value calculated according to the mixing ratio. As shown in Table 2, specific examples of solvents having a Hildebrand solubility parameter greater than or equal to 9.0 include tetrahydrofuran, chloroform, acetone, dichloromethane, dichloroethane, dioxane, isopropanol, ethanol, dimethylformamide, acetonitrile, acetic acid, dimethyl sulfoxide, methanol, ethylene glycol and water.

[0038] Table 2 δ: Hildebrand solubility parameter

[0039] The amount of solvent used is in the range of 25% to 2000% by weight of the total amount of the metal ion donor and the multidentate ligand, preferably 25% to 1000%, and this amount ratio can improve the production efficiency of the metal organic framework. It is worth noting that in the present invention, the amount of solvent used in the relevant embodiments using a turbine / stator type agitator can be less than that used in a vortex film type high-speed agitator (i.e., a higher concentration formulation can be used); for example, in some embodiments of the present invention, even if the amount of solvent used is not more than 100% of its weight (e.g., 25%-100%), a high-quality metal organic framework can be synthesized. By reducing the amount of solvent used, the production cost of the metal organic framework can be reduced and the impact of the synthesis on the environment can be reduced.

[0040] The above formula may further include other ingredients, such as a reaction accelerator. The reaction accelerator may be an alkaline or acidic substance, but is usually an alkaline substance, wherein alkaline reaction accelerators include diethylamine, triethylamine, 2,6-lutidine, pyridine, imidazole, potassium hydroxide and sodium hydroxide; acidic reaction accelerators include formic acid, acetic acid, trifluoroacetic acid, sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid. As additional ingredients, multiple reaction accelerators may be used in combination, and a reaction control agent may also be added.

[0041] Preferably, the above preparation process can be carried out at a specific reaction temperature. In some embodiments, the reaction temperature of the stirring process is below the standard boiling point of the solvent, that is, the stirring temperature is 80°C or lower, more preferably, 60°C or lower. In this way, the metal organic framework can be produced while maintaining an appropriate amount of solvent.

[0042] In the above preparation process, preferably, the speed of the agitator (i.e., the speed of the turbine) is 1,000-20,000 rpm, and more preferably, 5,000-15,000 rpm. The speed of the agitator can be appropriately adjusted according to the concentration of the formula, etc. If the speed is too low, the shear force applied to the reactants may be insufficient; but if the speed is too high, it may be difficult to control the temperature of the reaction system. Example

[0043] The following experiments can be used to further compare the preparation results of turbine / stator type high-speed agitators and non-turbine / stator type high-speed agitators.

[0044] Examples 1 to 30: Turbine / stator type high speed agitator The metal ion donor, multidentate ligand, solvent and optionally added reaction promoter shown in Table 3 are added to a batch reaction vessel; then, a turbine / stator type high-speed stirrer (homogeneous mixer MARK II 2.5 type or ) is stirred at high speed according to the reaction conditions shown in Table 3 to obtain a metal organic framework. Among them, it is worth noting that Neokaiser is a comb-tooth turbine and stator (such as Figure 4 shown).

[0045] Comparative Examples A1 to A33: High-speed stirring blade or stirrer The metal ion donor, multidentate ligand, solvent and optionally added reaction promoter shown in Table 4 are added to a batch reaction vessel; then, high-speed stirring is performed according to the reaction conditions shown in Table 4 using a high-speed stirring blade (homogenizer from Plemicus Machinery Co., Ltd.) or a commercially available stirrer.

[0046] Comparative Examples B1 to B39: Vortex Thin Film Type High Speed ​​Agitator The metal ion donor, multidentate ligand, solvent and optionally added reaction accelerator shown in Table 5 were added to a vortex thin film type high speed stirrer (Pramix Machinery Co., Ltd. 56-L type); then, high-speed stirring was performed according to the reaction conditions shown in Table 5.

[0047] Evaluate The samples prepared by the above method were dried under reduced pressure at room temperature for 24 hours using a vacuum dryer (MVD-300; As One Co., Ltd.), and the X-ray diffraction patterns of the dried samples were detected using an X-ray diffractometer (MiniFlex; Rigaku Co., Ltd.); in addition, some samples were heated to 140°C and vacuum dried for 4 hours (using a gas adsorption pretreatment device BERPREP-vacIII; MicrotracBEL), and their BET specific surface areas (N2; 77K) were measured using a gas adsorption instrument (BELSORP-miniX; MicrotracBEL).

[0048] By analyzing the X-ray diffraction spectrum for crystal peaks and BET specific surface area S BET The quality of the prepared metal-organic frameworks was evaluated by the size of the nanostructures, and the relevant results are summarized in Tables 3 to 5.

[0049] The following abbreviations are used in Tables 3 to 5: BTC:1,3,5-Benzenetricarboxylic acid (1,3,5-benzenetricarboxylic acid) 2,5-DHTP: dihydroxyterephthalic acid 2-Mim or Mim:2-methylimidazole 1,3-BDC or iBDC: Isophthalic acid DOBPDC:4,4'-dioxybiphenyl-3,3'-dicarboxylic acid Im: Imidazole BIm: Benzimidazole 1,4-BDC or pBDC: terephthalic acid IPA: isopropyl alcohol AcOH: Acetic acid (acetic acid) TEA:Triethylamine DEA: Diethanolamine INA:4-Picolidinecarboxylic acid ADC: acetylenic acid DOT: dihydroxy terephthalic acid BTC3Na: Trisodium 1,3,5-benzenetricarboxylate

[0050] Table 3

[0051] Table 4

[0052] Table 5

[0053] Comparing Table 3 and Table 4, it can be seen that compared with the use of high-speed stirring blades or stirrers, the use of a turbine / stator type high-speed stirrer can significantly shorten the reaction time for preparing metal organic frameworks and improve the quality of metal organic frameworks. Comparing Table 3 and Table 5, it can be seen that under large-scale preparation conditions, compared with the use of a rotating film type high-speed stirrer, the use of a turbine / stator type high-speed stirrer can synthesize metal organic frameworks of the same or higher quality.

[0054] Figure 5A : shows the X-ray diffraction pattern of the metal organic framework (HKUST-1) prepared in Example 1; Figure 5B The X-ray diffraction pattern of HKUST-1 prepared in Comparative Example A2 is shown in FIG. Figure 5B In the graph, the peak of the raw material copper (II) hydroxide (as indicated by the two arrows) still exists, which shows that the quality of the HKUST-1 obtained when the homogenizer is used is higher than that of the HKUST-1 prepared by the stirrer. Similarly, this difference is also reflected in the difference in the BET specific surface area.

[0055] Fig. 6A The X-ray diffraction pattern of the metal organic framework [MOF-74(Mg)] prepared in Example 7 is shown in FIG. Figure 6B The X-ray diffraction pattern of [MOF-74(Mg)] prepared in Comparative Example A4 is shown. By comparing the two, it can be seen that when conducting large-scale synthesis (the weight of the metal ion donor is about 2 kg), the former condition can successfully synthesize a high-quality metal organic framework, while the latter condition cannot successfully synthesize a metal organic framework. Similarly, this difference can also be seen in the comparison of BET specific surface area.

[0056] Fig. 7A ] shows the X-ray diffraction pattern of the metal organic framework (ZIF-8) prepared in Example 12; Figure 7B The X-ray diffraction pattern of ZIF-8 prepared in Comparative Example A13 is shown. Figure 7B In the graph, the peak of raw material zinc oxide can still be observed (as indicated by three arrows), which shows that the quality of ZIF-8 prepared by homogenizer is higher than that prepared by stirrer. This difference can also be observed by comparing BET specific surface area.

[0057] Fig. 8A ] shows the X-ray diffraction pattern of the metal organic framework (ZIF-67) prepared in Example 26; Figure 8B The X-ray diffraction pattern of ZIF-67 prepared in Comparative Example A32 is shown. Figure 8BIn the graph, the peak of raw material cobalt (II) hydroxide can still be observed (as indicated by an arrow). It can be seen that the quality of ZIF-67 prepared by homogenizing mixer is higher than that of ZIF-67 prepared by homogenizing disperser. Similarly, this difference can also be seen in the comparison of BET specific surface area.

[0058] In summary, relevant experiments show that when preparing various metal-organic frameworks, the use of a turbine / stator type high-speed agitator can significantly shorten the reaction time and prepare higher quality metal-organic frameworks compared to high-speed stirring blades or stirrers; at the same time, compared to a rotating thin film type high-speed agitator, the use of a turbine / stator type high-speed agitator can prepare metal-organic frameworks of equal or higher quality on a larger scale.

Claims

1. A method for preparing a metal organic framework, characterized in that: include: providing an agitator having a turbine and a stator surrounding the turbine; providing a formulation including a metal ion donor, a multidentate ligand, and a solvent; as well as The turbine is rotated relative to the stator in the agitator to generate a shear force between the turbine and the stator and apply the shear force to the formulation. 2 . The method according to claim 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 claim 1 or 2, wherein the solvent has a Hildebrand solubility parameter of greater than or equal to 9.

0.

4. The method according to claim 1 or 2, wherein the amount of the solvent used is in the range of 30 to 2000 weight % of the total amount of the metal ion donor and the multidentate ligand.

5. The process according to claim 1 or 2, wherein the process is carried out at a temperature below the normal boiling point of the solvent.

6. The 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 method of claim 1 or 2, wherein the metal organic framework is a porous coordination polymer.

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