A cobalt-based porous chiral metal-organic framework enzyme-mimic material, a preparation method and application thereof

Abstract

The application discloses a cobalt-based porous chiral metal-organic framework enzyme-mimic material and a preparation method and application thereof, relates to the technical field of chiral science, and the material is formed by one-pot coordination assembly with chiral H4L as a bridging ligand, 4, 4'-dipyridyl as an auxiliary ligand and cobalt as a metal salt; the application also provides a cobalt-based porous chiral metal-organic framework enzyme-mimic material prepared by the method and application thereof. The cobalt-based porous chiral metal-organic framework with unique cubic cavities, narrow open channels and chiral recognition sites and the enzyme-mimic structure characteristics can be assembled by coordination of the chiral ligand H4L, 4, 4'-dipyridyl and cobalt ions; the preparation method is simple, the conditions are mild and controllable, the yield is high and the method is easy to repeat. The material can separate enantiomers of chiral secondary alcohols with excellent enantioselectivity, size selectivity, substrate universality and recycling.

Description

Technical Field

[0001] This invention relates to the field of chiral materials technology, specifically to a cobalt-based porous chiral metal-organic framework enzyme-mimicking material, its preparation method, and its application. Background Technology

[0002] The preparation of chiral drugs and their synthetic intermediates with single configurations has become a research hotspot in the fields of medicine, chemistry, and materials. However, because the physical and chemical properties of a pair of enantiomers of a chiral molecule are almost identical in an achiral environment, they are particularly difficult to separate. Bioenzymes are a class of macromolecular materials that form unique chiral cavity structures and multiple chiral recognition sites through polypeptide chain folding, enabling them to recognize and separate enantiomers of chiral molecules with high enantioselectivity. However, due to the weak interactions between polypeptide chains, the structure of bioenzymes is easily affected by external environmental factors such as temperature, solvents, and acids / bases, leading to changes in their cavity structure and chiral environment, thus losing their ability to recognize and separate enantiomers. To meet the huge demand for chiral drugs and synthetic intermediates, it is currently essential to develop a new generation of chiral separation materials with enzyme-mimicking structures.

[0003] Chiral metal-organic frameworks (MOFs) combine the advantages of easily modifiable organic structures with the structural stability of inorganic structures. They can effectively mimic the unique chiral structures of biological enzymes and overcome the instability of these structures, thus providing a feasible research approach for developing novel, high-performance enzyme-mimicking chiral separation materials. Nevertheless, current technologies still present challenges in preparing chiral MOFs that highly mimic the unique chiral cavity structures and chiral microenvironments of biological enzymes, while exhibiting high enantioselectivity, size selectivity, and framework stability.

[0004] Chinese patent application CN112898585A discloses a chiral metal-organic framework material and its application in chiral chromatographic columns, belonging to the field of chiral resolution technology. This material uses the stable, porous Zr-based MOF material UiO-66-NH2 as the parent material and tartaric acid as the chiral source. A novel chiral UiO-tart MOF material was obtained through in-situ post-modification technology, and further configured into a chromatographic column, achieving good results in the resolution of various chiral molecules. However, the enantioselectivity, size selectivity, and framework stability of this material still need further improvement. Summary of the Invention

[0005] The technical problem to be solved by this invention is how to address the poor enantioselectivity, size selectivity and framework stability of existing enzyme-mimicking chiral separation materials.

[0006] The present invention solves the above-mentioned technical problems through the following technical means:

[0007] The first aspect of this invention provides a method for preparing a cobalt-based porous chiral metal-organic framework enzyme-mimicking material, comprising the following steps:

[0008] (1) Preparation of reaction solution: Chiral ligand H4L, auxiliary ligand 4,4'-bipyridine (bpy), and cobalt salt are dissolved in a solvent, then sealed in a reaction vessel and ultrasonically mixed until homogeneous; the structural formula of the chiral ligand H4L is as follows:

[0009] The solvent is a mixture of dimethylformamide (DMF) and water in a volume ratio of 1:(1-3);

[0010] (2) Crystallization reaction: The reaction solution prepared in step (1) is heated and reacted, and then cooled to obtain the crystal.

[0011] Beneficial Effects: This invention utilizes the chiral bridging ligand H4L, combined with a 4,4'-bipyridine (bpy) auxiliary bridging ligand, to coordinate and assemble with a cobalt metal salt to prepare a cobalt-based porous chiral metal-organic framework enzyme-mimicking material with the molecular formula [Co4L(bpy)2]. This material possesses a unique cubic cavity, abundant molecular channels, and multiple recognition sites, enabling efficient resolution of a pair of enantiomers of chiral molecules, exhibiting excellent enantioselectivity, size selectivity, and framework stability. Furthermore, the synthesis method is simple, the conditions are mild and controllable, and it can be prepared on a large scale.

[0012] Preferably, the molar ratio of the chiral ligand H4L, the auxiliary ligand bpy, and the cobalt salt is (3-1):(1-3):6.

[0013] Preferably, the molar ratio of the chiral ligand H4L, the auxiliary ligand bpy, and the cobalt salt is 1:1:2.

[0014] Beneficial effects: When the molar ratio of chiral ligand H4L, auxiliary ligand bpy, and cobalt salt is 1:1:2, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material has a high crystal yield and can be prepared repeatedly in large quantities.

[0015] Preferably, the cobalt salt is one of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, and cobalt acetate dihydrate.

[0016] Preferably, the solvent is a mixture of dimethylformamide (DMF) and water in a volume ratio of 1:1.

[0017] Preferably, the heating reaction is carried out at a temperature of 60-80°C for a duration of 24 hours or more.

[0018] A second aspect of the present invention provides a cobalt-based porous chiral metal-organic framework enzyme-mimicking material (microcrystalline structure) prepared by the above method.

[0019] Beneficial Effects: The cobalt-based porous chiral metal-organic framework enzyme-mimicking material provided by this invention possesses a cuboid chiral cavity with dimensions of 0.7 nm × 0.9 nm × 1.1 nm and two narrow open molecular channels with dimensions of 0.55 nm × 0.45 nm and 0.36 nm × 1.1 nm, respectively. The chiral cavity is surrounded by four hydrophilic amide groups, six hydrophobic methylene groups, and ten hydrophobic benzene rings. This unique structural feature is highly similar to the structure of biological enzymes that simultaneously possess a chiral internal cavity, recognition functional sites, and molecular transport channels. Therefore, it is suitable as an enzyme-mimicking chiral material to selectively recognize and distinguish enantiomers of chiral molecules, providing conditions for chiral separation. Moreover, the existence of this unique and precise chiral environment and porous structure also contributes to a deeper understanding of the intrinsic relationship between enzyme-mimicking chiral materials and chiral separation performance.

[0020] Preferably, the cell parameters of the cobalt-based porous chiral metal-organic framework enzyme-mimicking material are as follows: α=β=γ=90°,

[0021] A third aspect of the present invention proposes the application of cobalt-based porous chiral metal-organic framework enzyme-mimicking materials prepared by the above method in the separation of enantiomers of different types of chiral alcohol compounds.

[0022] Beneficial effects: The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of this invention can separate racemic aliphatic secondary alcohols and racemic aromatic secondary alcohols, and has excellent enantioselectivity, substrate universality, size selectivity and recyclability.

[0023] Preferably, the enantiomer separation operation of chiral alcohol compounds includes the following steps:

[0024] (1) Pretreatment: The crystals of cobalt-based porous chiral metal-organic framework enzyme-mimicking material were subjected to solvent exchange treatment with anhydrous diethyl ether;

[0025] (2) Separation of enantiomers: The cobalt-based porous chiral metal-organic framework enzyme-mimicking material crystals after solvent exchange treatment in step (1) were immersed in a diethyl ether solution of chiral alcohols for full adsorption. Then, centrifugation was performed, and the chiral small molecule secondary alcohols on the surface of the crystals were washed away with diethyl ether. Then, the chiral small molecule secondary alcohols adsorbed inside the crystals were extracted with acetone. Finally, their ee values ​​were characterized.

[0026] Preferably, the chiral alcohol compounds include 2-butanol, 3-methyl-2-butanol, 1-phenylethanol, 1-(4-methylphenyl)ethanol, 1-(2-methylphenyl)ethanol, 1-(4-chlorophenyl)ethanol, and 1-(4-fluorophenyl)ethanol.

[0027] The advantages of this invention are:

[0028] 1. This invention utilizes the chiral bridging ligand H4L and the auxiliary ligand bpy to perform a one-pot coordination assembly with cobalt salts to prepare cobalt-based porous chiral metal-organic framework enzyme-mimicking materials with crystalline structures. The synthesis method is simple, the conditions are mild and controllable, and it can be prepared on a large scale.

[0029] 2. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material provided by this invention possesses a unique cuboid chiral cavity, narrow molecular channels, and multiple recognition sites, similar to the unique chiral microstructure of biological enzymes. It is suitable for the differentiation and recognition of chiral small molecule compounds, exhibiting excellent enantioselectivity, substrate universality, and size selectivity in the separation of enantiomers of chiral secondary alcohol molecules. In particular, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material has a well-defined microstructure, which is helpful for studying the intrinsic relationship between the structure of enzyme-mimicking chiral separation materials and their enantioselective separation performance.

[0030] 3. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material provided by this invention has good framework stability, can continuously separate chiral 2-butanol multiple times, maintains the separation performance unchanged, and has good recyclability. Attached Figure Description

[0031] Figure 1 This is a diagram illustrating the connection between organic ligands and metal ions in the cobalt-based porous chiral metal-organic framework enzyme-mimicking material of Example 2 of the present invention.

[0032] Figure 2 This is a three-dimensional structural diagram of the cobalt-based porous chiral metal-organic framework enzyme-mimicking material in Example 2 of the present invention;

[0033] Figure 3 This is a diagram of the internal cavity and chiral microenvironment of the enzyme-mimicking material based on a cobalt-based porous chiral metal-organic framework in Example 2 of the present invention.

[0034] Figure 4 The image shows the HPLC results of the separation of 2-butanol using cobalt-based porous chiral metal-organic framework enzyme-mimicking material in Example 13 of this invention, where A is the spectrum of the racemic sample before separation; and B is the spectrum of the chiral sample after separation.

[0035] Figure 5The image shows the HPLC results of the separation of 1-phenylethanol using cobalt-based porous chiral metal-organic framework enzyme-mimicking material in Example 13 of this invention, where A is the spectrum of the racemic sample before separation; and B is the spectrum of the chiral sample after separation.

[0036] Figure 6 This is a diagram showing the preparation process and structure of the cobalt-based porous chiral metal-organic framework enzyme-mimicking material in Example 2 of the present invention. Detailed Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0038] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.

[0039] Unless otherwise specified in the embodiments, the techniques or conditions described in the literature in this field or in accordance with the product manual may be followed.

[0040] Example 1:

[0041] The synthesis route and specific steps of the S-configuration chiral ligand H4L are as follows:

[0042]

[0043] (1) L-Aspartic acid methyl ester (5.6 g, 35 mmol) was dissolved in dichloromethane (30 mL) and slowly added to Et3N (6.5 mL, 47 mmol) at 0 °C. Then, terephthaloyl chloride (3.2 g, 16 mmol) was slowly added to the mixture. The reaction mixture was reacted for 3 h at 60 °C. The reaction mixture was concentrated under reduced pressure and poured into 100 mL of water. The organic phase was extracted with ethyl acetate, washed with 2 M HCl and saturated NaHCO3 solution, respectively, dried with Na2SO4, and then concentrated under reduced pressure to obtain 5.8 g of pale yellow esterified ligand product L-Me4, with a yield of about 80%.

[0044] (2) The L-Me4 (6.3 g, 14 mmol) and LiOH (1.7 g, 71 mmol) from step (1) were dissolved in a mixed solvent of THF (24 mL) and H2O (6 mL). The mixture was stirred at 80 °C for 12 h. The reaction mixture was concentrated under reduced pressure, the residue was diluted with H2O, and then acidified with 2 M HCl. The white precipitate was collected by filtration, washed with water, and dried to finally obtain 5.3 g of white powder of the S-configuration chiral ligand H4L, with a yield of 95%.

[0045] Example 2:

[0046] Synthesis of cobalt-based porous chiral metal-organic framework enzyme-mimicking materials:

[0047] Cobalt chloride hexahydrate (19.0 mg, 0.08 mmol), S-configuration chiral ligand H4L (15.8 mg, 0.04 mmol), and auxiliary ligand bpy (6.2 mg, 0.04 mmol) in a molar ratio of 2:1:1 were dissolved in 20 mL of a 1:1 mixture of DMF and H2O. The prepared crystallization reaction solution was heated to 70 °C and maintained for 72 h to obtain brick-red, strip-shaped, block-shaped cobalt-based porous chiral metal-organic framework enzyme-mimicking material with a yield of approximately 75%.

[0048] Example 3:

[0049] The only difference from Example 2 is that cobalt chloride hexahydrate in Example 2 is replaced with an equal amount of cobalt nitrate hexahydrate, while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained with a yield of about 70%.

[0050] Example 4:

[0051] The only difference from Example 2 is that the cobalt chloride in Example 2 is replaced with an equal amount of cobalt acetate dihydrate, while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained with a yield of about 72%.

[0052] Example 5:

[0053] The only difference from Example 2 is that the 20 mL DMF and H2O in the volume ratio of 1:1 in Example 2 is replaced with 20 mL DMF and H2O in the volume ratio of 1:2. The other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained, but the yield is reduced to about 50%.

[0054] Example 6:

[0055] The only difference from Example 2 is that the 20 mL DMF and H2O in the volume ratio of 1:1 in Example 2 is replaced with 20 mL DMF and H2O in the volume ratio of 1:3. The other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained, but the yield is reduced to about 30%.

[0056] Example 7:

[0057] The only difference from Example 2 is that the "molar ratio of 2:1:1" in Example 2 is replaced with "molar ratio of 6:1:3", while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained with a yield of about 45%.

[0058] Example 8:

[0059] The only difference from Example 2 is that the "molar ratio of 2:1:1" in Example 2 is replaced with "molar ratio of 6:3:1", while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained with a yield of about 50%.

[0060] Example 9:

[0061] The only difference from Example 2 is that the heating time of the crystallization reaction solution prepared in Example 2 is adjusted to 24 hours, while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained, but the yield is reduced to about 25%.

[0062] Example 10:

[0063] The only difference from Example 2 is that "70℃" in Example 2 is changed to "60℃", while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained, but the yield is reduced to about 55%.

[0064] Example 11:

[0065] The only difference from Example 2 is that "70℃" in Example 2 is changed to "80℃", while the other reaction conditions remain unchanged. The cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention can also be obtained, but the yield is reduced to about 65%.

[0066] Example 12:

[0067] The only difference from Example 2 is that the S-configuration chiral ligand H4L used in Example 2 is replaced with the R-configuration chiral ligand H4L, with the following structural formula: If the remaining reaction conditions are kept constant, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the R-configuration of this invention can be obtained.

[0068] Single-crystal structure characterization and analysis of cobalt-based porous chiral metal-organic framework enzyme-mimicking materials:

[0069] The single crystals of the cobalt-based porous chiral metal-organic framework enzyme-mimicking material in Example 2 were tested and analyzed by synchrotron radiation. Their unit cell parameters were: orthogonal Pccn space group. α=β=γ=90°, Single-crystal structure analysis reveals that this single-crystal material is a porous chiral metal-organic framework with a unique chiral cuboid cavity, abundant molecular channels, and multiple recognition sites. Its asymmetric unit content is half that of its molecular formula [Co4L(bpy)2], containing half a fully deprotonated ligand L, one bpy molecule, and two cobalt ions. The auxiliary ligand bpy molecule first connects the cobalt ions in a linear coordination manner to form a one-dimensional chain-like Co(bpy) structure. Then, each ligand L uses its four carboxyl groups to connect four surrounding one-dimensional Co(bpy) chains in a monodentate chelate manner, forming a three-dimensional porous metal-organic framework material. Figure 1 This describes the coordination linkage mode of ligand L in cobalt-based porous chiral metal-organic framework enzyme-mimicking materials. Figure 2 This describes the three-dimensional structure of a cobalt-based porous chiral metal-organic framework enzyme-mimicking material. Specifically, the porous structure contains two types of narrow open channels with dimensions of 0.55 nm × 0.45 nm and 0.36 nm × 1.1 nm, providing pathways for guest molecule transport. These narrow channels also allow for selective adsorption of different guest molecule sizes. More significantly, eight hexa-linked Co(CO4N2) metal cluster nodes, two L ligands, and four bpy molecules collectively form a rectangular chiral cavity measuring 1.1 nm × 0.7 nm × 0.9 nm, providing space to accommodate guest molecules. Surrounding the chiral cavity are densely embedded four hydrophilic amide groups, six hydrophobic methylene groups, and ten hydrophobic benzene rings, providing functional sites for recognizing and distinguishing enantiomers of chiral molecules. Figure 3 The internal cavity structure and chiral recognition sites of cobalt-based porous chiral metal-organic framework enzyme-mimicking materials.

[0070] Example 13:

[0071] The application of cobalt-based porous chiral metal-organic framework enzyme-mimicking materials in the enantioselective separation of chiral secondary alcohol compounds, with the following specific steps:

[0072] (1) Pretreatment of cobalt-based porous chiral metal-organic framework enzyme-mimicking material crystals: The solvent molecules such as DMF and H2O encapsulated in the cobalt-based porous chiral metal-organic framework enzyme-mimicking material crystals in Example 2 were exchanged multiple times with anhydrous diethyl ether.

[0073] (2) Separation of enantiomers: The cobalt-based porous chiral metal-organic framework enzyme-mimicking material crystals treated in step (1) were placed in a racemic diethyl ether solution of chiral secondary alcohol compounds for 5 h for adsorption; then the crystals were centrifuged and washed; finally, the chiral secondary alcohol molecules adsorbed in the crystal pore structure were extracted with acetone, and the enantiomeric excess value (ee value) of the extracted chiral secondary alcohol molecules or their derivatives was characterized by high performance liquid chromatography.

[0074] Table 1 shows the structures and separation results of different types and sizes of chiral secondary alcohols enantioselectively separated by cobalt-based porous chiral metal-organic framework enzyme-mimicking materials. Figure 4 and Figure 5 The results show the enantioselective separation of the substrates 2-butanol and 1-phenylethanol by cobalt-based porous chiral metal-organic framework enzyme-mimicking materials.

[0075] Table 1: Structures and separation results of chiral secondary alcohols enantioselectively separated by cobalt-based porous chiral metal-organic framework enzyme-mimicking materials.

[0076]

[0077] As shown in Table 1, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material can separate small aliphatic 2-butanol and 3-methyl-2-butanol with a high enantiomeric excess (ee value) of up to 99.9%; it can also separate larger aromatic 1-phenylethanol and its derivatives with a moderate ee value, reaching up to 70.1%; however, it has no separation effect on the even larger 1-naphthylethanol. These results demonstrate that the cobalt-based porous chiral metal-organic framework enzyme-mimicking material exhibits excellent enantioselectivity, size selectivity, and substrate suitability for the enantiomeric separation of chiral secondary alcohols.

[0078] Example 14:

[0079] Cyclic enantiomeric separation experiments using cobalt-based porous chiral metal-organic framework enzyme-mimicking materials:

[0080] The cobalt-based porous chiral metal-organic framework enzyme-mimicking material crystals obtained from solvent exchange in Example 13 were placed in a diethyl ether solution of racemic 2-butanol, and then the enantiomer separation experiment of step (2) in Example 13 was repeated four times. The separation results showed that the ee value of optically pure 2-butanol obtained each time could be maintained above 99%, indicating that this cobalt-based porous chiral metal-organic framework enzyme-mimicking material has excellent recycling performance and is a potentially usable chiral separation material.

[0081] Comparative Example 1:

[0082] The only difference between this comparative example and Example 2 is that the 20 mL DMF and H2O in the volume ratio of 1:1 in Example 2 is replaced with 20 mL DMF and H2O in the volume ratio of 1:4. The other reaction conditions remain unchanged. Therefore, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention cannot be obtained.

[0083] Comparative Example 2:

[0084] The only difference between this comparative example and Example 2 is that the 20 mL DMF and H2O in the volume ratio of 1:1 in Example 2 is replaced with 20 mL DMF and H2O in the volume ratio of 3:1. The other reaction conditions remain unchanged. Therefore, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention cannot be obtained.

[0085] Comparative Example 3:

[0086] The only difference between this comparative example and Example 2 is that the heating time of the crystallization reaction solution prepared in Example 2 is adjusted to 12 hours, while the other reaction conditions remain unchanged. Therefore, the cobalt-based porous chiral metal-organic framework enzyme-mimicking material of the present invention cannot be obtained.

[0087] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a cobalt-based porous chiral metal-organic framework enzyme-mimicking material, characterized in that, Includes the following steps: (1) Preparation of reaction solution: Chiral ligand H4L, auxiliary ligand 4,4'-bipyridine bpy, and cobalt salt are dissolved in solvent, then sealed in a reaction vessel and ultrasonically mixed until homogeneous; the structural formula of the chiral ligand H4L is as follows: or The solvent is a mixture of dimethylformamide and water in a volume ratio of 1:(1-3); (2) Crystallization reaction: The reaction solution prepared in step (1) is heated to react, and then cooled to obtain the crystal; The cobalt-based porous chiral metal-organic framework enzyme-mimicking material has the molecular formula [Co4L(bpy)2], and its unit cell parameters are as follows: orthogonal. Pccn Space group, a = 9.4202(2)Å, b = 15.7948(4) Å, c =22.9268(6) Å, α = β = γ = 90°, V = 3411.28(14) Å 3 The heating reaction is carried out at a temperature of 60-80℃ for a duration of 24 hours or more.

2. The method for preparing cobalt-based porous chiral metal-organic framework enzyme-mimicking materials according to claim 1, characterized in that, The molar ratio of the chiral ligand H4L, the auxiliary ligand 4,4'-bipyridine bpy, and the cobalt salt is (3-1):(1-3):

6.

3. The method for preparing cobalt-based porous chiral metal-organic framework enzyme-mimicking materials according to claim 1 or 2, characterized in that, The cobalt salt is one of cobalt chloride hexahydrate, cobalt nitrate hexahydrate, and cobalt acetate dihydrate.

4. The method for preparing cobalt-based porous chiral metal-organic framework enzyme-mimicking materials according to claim 3, characterized in that, The solvent is a mixture of dimethylformamide and water in a volume ratio of 1:

1.

5. Cobalt-based porous chiral metal-organic framework enzyme-mimicking materials prepared by the preparation method according to any one of claims 1-4.

6. The application of cobalt-based porous chiral metal-organic framework enzyme-mimicking materials prepared by the preparation method according to any one of claims 1-4 in the separation of enantiomers of chiral alcohol compounds.

7. The application according to claim 6, characterized in that, The enantiomer separation process for chiral alcohols includes the following steps: (1) Pretreatment: The crystals of cobalt-based porous chiral metal-organic framework enzyme-mimicking material were subjected to solvent exchange treatment with anhydrous diethyl ether; (2) Separation of enantiomers: The cobalt-based porous chiral metal-organic framework enzyme-mimicking material crystals after solvent exchange treatment in step (1) were immersed in a diethyl ether solution of chiral alcohols for full adsorption. Then, centrifugation was performed, and the chiral small molecule secondary alcohols on the surface of the crystals were washed away with diethyl ether. Then, the chiral small molecule secondary alcohols adsorbed inside the crystals were extracted with acetone. Finally, their ee values ​​were characterized.

8. The application according to claim 7, characterized in that, The chiral alcohols include 2-butanol, 3-methyl-2-butanol, 1-phenylethanol, 1-(4-methylphenyl)ethanol, 1-(2-methylphenyl)ethanol, 1-(4-chlorophenyl)ethanol, and 1-(4-fluorophenyl)ethanol.

9. The application according to claim 8, characterized in that, The chiral alcohols include 2-butanol.

10. The application according to claim 8, characterized in that, The chiral alcohols include 3-methyl-2-butanol.

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