Zeolite mimic metal-organic framework and manufacturing method therefor

Abstract

The present invention relates to a zeolite mimic metal-organic framework and a manufacturing method therefor. The zeolite mimic metal-organic framework according to one embodiment of the present invention comprises a compound of chemical formula 1: [Chemical formula 1] M is a central metal, and R includes an imidazole group-containing R1 and / or R2.

Description

Zeolite-mimicking metal-organic framework and method for manufacturing the same

[0001] The present invention relates to a zeolite-mimicking metal-organic framework and a method for manufacturing the same.

[0002] Machines are defined by the interaction of links and joints that enable mechanical movement, and they have undergone significant evolutionary processes over time. This evolution, deeply rooted in history, has met critical requirements in various fields ranging from architecture to mechanical engineering. The fundamental principles of machine design are based on the fact that mechanical motion occurs within a series of mechanical components, such as Watt, Scott-Russell, Sarrus, Bennett, Hoberman, and Klann links. Each link provides unique mobility, which is essential for specific machine functions. Machines have also evolved on various scales, now reaching the molecular level. In particular, molecular machines consist of stators and rotators, and their connection determines operation and function. As the list of these molecular machines—including robotic arms, revolving doors, gears, shuttles, elevators, ratchets, motors, and pumps—grows, their importance in fields such as nano and soft robotics, molecular transport, and catalysis has been highlighted. However, developing nanomachines with complex solid-state mechanical connections remains a difficult challenge.

[0003] Metal-organic frameworks (MOFs) can serve as an ideal platform to facilitate the fabrication of solid-state nanomachines, allowing molecular machines to be integrated as mechanical components into pre-developed structures. A notable recent example involved introducing multiple dynamic components into MOFs using pillar ligands, in which the rotational motion of the inserted machines was maintained in the solid state. Despite these efforts, instances linking the machine-like behavior of MOFs to mechanical properties have been very rare, primarily because MOFs have not yet inherently exhibited such behavior.

[0004] The aforementioned background technology is one that the inventor possessed or acquired in the process of deriving the disclosure of the present invention, and it cannot be considered as prior art disclosed to the general public prior to the filing of this application.

[0005] The present invention aims to solve the aforementioned problems, and the objective of the present invention is to provide a zeolite-mimicking metal-organic framework capable of performing mechanical functions in a solid state and a method for manufacturing the same.

[0006] However, the problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned problems will be clearly understood by those skilled in the art from the description below.

[0007] A zeolite-mimicking metal-organic framework according to one embodiment of the present invention comprises the following chemical formula 1:

[0008] [Chemical Formula 1]

[0009]

[0010] The above M is a central metal, and

[0011] The above R comprises R1, R2, or both containing an imidazole group.

[0012] A zeolite-mimicking metal-organic framework according to another embodiment of the present invention comprises the following chemical formula 2:

[0013] [Chemical Formula 2]

[0014]

[0015] The above M is a central metal, and

[0016] The above R comprises R1, R2, or both containing an imidazole group.

[0017] In one embodiment, the central metal may comprise at least one selected from the group consisting of zinc (Zn), cobalt (Co), iron (Fe), cadmium (Cd), copper (Cu), and manganese (Mn).

[0018] In one embodiment, the R1 may be selected from the following structures:

[0019]

[0020] In one embodiment, the R2 may be selected from the following structures:

[0021]

[0022] In one embodiment, when the zeolite-mimicking metal-organic framework includes R1, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) is 100° to 105°, and when the zeolite-mimicking metal-organic framework includes R2, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) may be 93° to 97°.

[0023] A method for manufacturing a zeolite-mimicking metal-organic framework according to another embodiment of the present invention comprises the steps of: preparing a mixed solution by mixing a metal compound containing a metal ion, an imidazole, an amine, a hydroxyl-based additive, and a solvent; and manufacturing a metal-imidazole from the mixed solution through a solvothermal reaction.

[0024] In one embodiment, the metal compound may comprise at least one selected from the group consisting of a zinc compound, a cobalt compound, an iron compound, a cadmium compound, a copper compound, and a manganese compound.

[0025] The above zinc compound is zinc trifluoro-methasulfonate , zinc nitrate (Zn(NO3)2), zinc acetate, ), zinc trifluoromethanesulfonate, zinc acetate, ), zinc chloride and zinc fluoride hydrate (ZnF2), zinc dichloride It may include at least one selected from a group consisting of

[0026] The above cobalt compound may comprise at least one selected from the group consisting of cobalt chloride (CoCl2), cobalt fluoride (CoF2), cobalt hydroxide (Co(OH)2) and cobalt sulfate (CoSO4).

[0027] The above iron compounds are iron sulfate (FeSO4), iron nitrate, It may include at least one selected from the group consisting of iron chloride (FeCl3), iron bromide (FeBr2, FeBr3), and iron hydroxide (Fe(OH)2).

[0028] The above cadmium compound may include at least one selected from the group consisting of cadmium fluoride (CdF2), cadmium chloride (CdCl2), cadmium bromide (CdBr2), cadmium iodide (CdI2), cadmium nitrate (Cd(NO3)2), and cadmium hydrate (Cd(OH)2).

[0029] The copper compound may comprise at least one selected from the group consisting of copper sulfide (CuS), copper sulfate (CuSO4), copper acetate (Cu(CO2CH3)2), copper chloride (CuCl2), copper iodide (CuI2), and copper hydroxide (Cu(OH)2).

[0030] The above manganese compound may include at least one selected from the group consisting of manganese sulfate (MnSO4), manganese chloride (MnCl2), and manganese nitrate (Mn(NO3)2).

[0031] In one embodiment, amine and hydroxyl-based additives may be used during the solvothermal reaction.

[0032] In one embodiment, the amine and hydroxyl-based additives are triethylamine (TEA), benzylamine (BA), piperidine (PD), ethylenediamine (EDA), piperazine (PZ), benzene-1,4-diamine (BD), and alpha-cyclodextrin. , beta cyclodextrin , gamma cyclodextrin It may include at least one selected from a group consisting of

[0033] In one embodiment, the solvent may include an amide and a pyrrolidine-based organic solvent.

[0034] In one embodiment, the amide and pyrrolidine-based organic solvent may comprise at least one selected from the group consisting of dimethylformamide (N,N-Dimethylformamide; DMF), diethylformamide (N,N-Diethylformamide; DEF), methylpyrrolidine (1-Methylpyrrolidine), dibutylformamide (N,N-Dibutylformamide; DBF), diethylbenzamide (N,N-Diethylbenzamide; DEB), diethylacetamide (N,N-diethylacetamide; DEA), methylformamide (N-methylformamide; NMF), and dimethylacetamide (N,N-dimethylacetamide; DMA).

[0035] In one embodiment, the imidazole may comprise the following R1, R2, or both.

[0036] In one embodiment, the R1 may be selected from the following structures:

[0037]

[0038] In one embodiment, the R2 may be selected from the following structures:

[0039]

[0040] In one embodiment, the mixed solution may be a mixture of metal ions and imidazole in a molar ratio of 1:0.02 to 1:20.

[0041] In one embodiment, the solvothermal reaction may be carried out for 12 to 240 hours at a temperature of 20 to 150 ℃.

[0042] According to another embodiment of the present invention, a zeolite-mimicking metal-organic framework (MOF) in a solid-state nanomechanical system utilizing a zeolite-mimicking imidazolate framework (ZIFs) includes a component that implements mechanical behavior similar to a slider-crank mechanism, which is not present in the prior art, thereby exhibiting effects of flexible OTO angle control and energy absorption. It exhibits flexible mechanical behavior based on molecular movement, and can precisely model behavior similar to a macromachine through mathematical modeling.

[0043] In addition, when bulky chemical functional groups are introduced into the ZIF structure, these functional groups act as stoppers for macro-mechanical devices, exhibiting unique mechanical properties. Furthermore, gis-ZIF-1 exhibits very low Young's modulus and shear modulus, making it a suitable candidate for applications requiring energy absorption.

[0044] Figure 1 is a diagram showing the structural similarity between gis-ZIF-1 and zeolite according to an embodiment of the present invention.

[0045] FIG. 2 is a diagram showing a ball and rod model of a gis-ZIF-1 single crystal structure according to an embodiment of the present invention.

[0046] Figure 3 shows the relative change of parameters a and c according to temperature of gis-ZIF-1 according to an embodiment of the present invention.

[0047] Figure 4 shows the relative change in the volume of a unit cell according to the temperature of gis-ZIF-1 according to an embodiment of the present invention.

[0048] FIG. 5 is a diagram comparing the length change inside the rigid mechanical components of gis-ZIF-1 according to an embodiment of the present invention and the angle between these components.

[0049] FIG. 6 is a diagram showing a CBU as a mechanical component inside the gis topology of the gis-ZIF-1 structure according to an embodiment of the present invention.

[0050] Figure 7 shows the mechanical movement of the ZIF machine in the gis-ZIF-1 structure according to an embodiment of the present invention, and the SCXRD analysis according to temperature. This is a diagram showing the change of.

[0051] FIG. 8 is a 2D projection model of gis-ZIF-1 according to an embodiment of the present invention and FIG. 9 is This is a diagram showing the mathematical analysis of ZIF dynamics through a comparison of the experimental and calculated relationships between the parameters.

[0052] FIG. 10 shows the rotation angle as a function of temperature of gis-ZIF-1 according to an embodiment of the present invention. and OTO angle This is a diagram showing a comparison of

[0053] FIG. 11 shows the rotation angle of gis-ZIF-1 and gis-zeolite according to an embodiment of the present invention. and OTO angle This is a diagram comparing mechanics from the side.

[0054] FIG. 12 is a diagram showing gis-ZIF-2 with adjusted mechanical components by attaching functional groups to gis-ZIF-1 molecular links according to an embodiment of the present invention.

[0055] FIG. 13 is a diagram showing the extended structure of gis-ZIF-1 (left) and gis-ZIF-2 (right) at 100 K according to an embodiment of the present invention.

[0056] FIG. 14 shows the rotation angles of gis-ZIF-1 and gis-ZIF-2 according to an embodiment of the present invention. and OTO angle This is a diagram showing the correlation between them.

[0057] Figure 15 is a diagram comparing the relative potential energy profiles per Zn for simulated ZIF dynamics.

[0058] FIG. 16 is a diagram showing 3D surface and 2D polar coordinate plots of Young's modulus, linear compressibility, maximum (orange) and minimum (green) shear modulus, and Poisson's ratio of gis-ZIF-1 according to an embodiment of the present invention.

[0059] FIG. 17 is a figure showing the relationship between the maximum Young's modulus and the shear modulus of gis-ZIF-1, ZIF, and carboxylate-based MOF according to an embodiment of the present invention.

[0060] Hereinafter, embodiments are described in detail with reference to the attached drawings. However, various modifications may be made to the embodiments, and thus the scope of the patent application is not limited or restricted by these embodiments. It should be understood that all modifications, equivalents, and substitutions to the embodiments are included within the scope of the rights.

[0061] The terms used in the embodiments are for illustrative purposes only and should not be interpreted as intended to be limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0062] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the embodiments pertain. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0063] In addition, when describing with reference to the attached drawings, identical components are assigned the same reference numeral regardless of drawing symbols, and redundant descriptions thereof are omitted. In describing the embodiments, if it is determined that a detailed description of related prior art could unnecessarily obscure the essence of the embodiments, such detailed description is omitted.

[0064] In addition, terms such as first, second, A, B, (a), (b), etc. may be used when describing the components of the embodiments. These terms are used merely to distinguish the components from other components, and the essence, order, or sequence of the components is not limited by the terms.

[0065] Components included in any one embodiment and components having common functions shall be described using the same names in other embodiments. Unless otherwise stated, the description in any one embodiment may also apply to other embodiments, and specific descriptions shall be omitted to the extent of overlap.

[0066] Hereinafter, the zeolite-mimicking metal-organic framework of the present invention and the method for manufacturing the same will be described in detail with reference to the examples and drawings. However, the present invention is not limited to these examples and drawings.

[0067] A zeolite-mimicking metal-organic framework according to one embodiment of the present invention aims to utilize zeolite-like MOFs, specifically zeolite imidazolate frameworks (ZIFs), for mechanical functions in the solid state. Due to their deformation capabilities and diverse topologies, ZIFs can serve as an ideal foundation for designing nanoscale machines. We introduce a series of ZIFs featuring a gis topology that incorporates mechanical connections where composite building units (CBUs) function as mechanical components. Within these ZIFs, thermal reactions exhibit stiffness in the CBUs and highlight Zn atomic sites as critical joints, resulting in unique co-rotational motion. Furthermore, the functional group type of the imidazolate linker can significantly influence these ZIF kinetics. These unique mechanical characteristics allow for selective deformation in gis-ZIFs, leading to anisotropic mechanical properties. In particular, these ZIF kinetics resemble a slider-crank mechanism, which has not been demonstrated in conventional flexible MOFs. These ZIF machines, utilizing specific mechanical components, are expected to have the potential to provide superior mechanical capabilities by reshaping the adaptive solids field.

[0068] A zeolite-mimicking metal-organic framework according to one embodiment of the present invention comprises the following chemical formula 1:

[0069] According to one embodiment, the zeolite-mimicking metal-organic framework may be formed by repeating the structure of Chemical Formula 1 below.

[0070] [Chemical Formula 1]

[0071]

[0072] The above M is a central metal, and

[0073] The above R comprises R1, R2, or both containing an imidazole group.

[0074] In one embodiment, the central metal may comprise at least one selected from the group consisting of zinc (Zn), cobalt (Co), iron (Fe), cadmium (Cd), copper (Cu), and manganese (Mn).

[0075] Preferably, the central metal may be zinc (Zn).

[0076] In one embodiment, the R1 may be selected from the following structures:

[0077]

[0078] In one embodiment, the R2 may be selected from the following structures:

[0079]

[0080] Preferably, a zeolite-mimicking metal-organic framework according to one embodiment of the present invention may comprise the following formula 1-1, in which the central metal having a structure similar to a tetrahedron-based ZIF and a zeolite is zinc (Zn) and includes an imidazolate ligand:

[0081] [Chemical Formula 1-1]

[0082]

[0083] In one embodiment, when the zeolite-mimicking metal-organic framework includes R1, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) is 100° to 105°, and when R2 is included in the zeolite-mimicking metal-organic framework, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) may be 93° to 97°.

[0084] In one embodiment, the zeolite-mimicking metal-organic framework comprising the formula 1-1 has a rotation angle ( As ) increases, the OTO angle( ) may be increasing.

[0085] The above rotation angle ( ) represents the angle between the four-membered rings (4MR) and the helical chain in 2D.

[0086] The above OTO angle ( ) can be called the tetrahedral angle and represents the angle between the 4MR and helical chains in the 3D phase of the actual molecule.

[0087] As the temperature increases, two types of angles ( and ) increases, and the increased OTO angle( The position of ) is the rotation angle( It coincides with the position of ), and the change may show a similar trend.

[0088] Meanwhile, in the case of gis-zeolite, the rotation angle ( ) does not change.

[0089] Accordingly, the zeolite-mimicking metal-organic framework according to one embodiment of the present invention may exhibit mechanical operation in response to temperature changes.

[0090] A zeolite-mimicking metal-organic framework according to another embodiment of the present invention comprises the following chemical formula 2:

[0091] According to one embodiment, the zeolite-mimicking metal-organic framework may be formed by repeating the structure of Chemical Formula 2 below.

[0092] [Chemical Formula 2]

[0093]

[0094] The above M is a central metal, and

[0095] The above R comprises R1, R2, or both containing an imidazole group.

[0096] In one embodiment, the central metal may comprise at least one selected from the group consisting of zinc (Zn), cobalt (Co), iron (Fe), cadmium (Cd), copper (Cu), and manganese (Mn).

[0097] Preferably, the central metal may be zinc (Zn).

[0098] In one embodiment, the R1 may be selected from the following structures:

[0099]

[0100] In one embodiment, the R2 may be selected from the following structures:

[0101]

[0102] A zeolite-mimicking metal-organic framework according to one embodiment of the present invention may comprise the following formula 2-1, in which the central metal is zinc (Zn) and includes an imidazolate ligand:

[0103] [Chemical Formula 2-1]

[0104]

[0105] In one embodiment, when the zeolite-mimicking metal-organic framework includes R1, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) may be 100° to 105°.

[0106] The above rotation angle ( ) represents the angle between the four-membered rings (4MR) and the helical chain in 2D.

[0107] The above OTO angle ( ) can be called the tetrahedral angle and represents the angle between the 4MR and helical chains in the 3D phase of the actual molecule.

[0108] As the temperature increases, two types of angles ( and ) increases, and the increased OTO angle( The position of ) is the rotation angle( It coincides with the position of ), and the change may show a similar trend.

[0109] Meanwhile, in the case of gis-zeolite, the rotation angle ( ) does not change.

[0110] Accordingly, the zeolite-mimicking metal-organic framework according to one embodiment of the present invention may exhibit mechanical operation in response to temperature changes.

[0111] A zeolite-mimicking metal-organic framework according to one embodiment of the present invention may comprise the following formula 2-2, in which the central metal is zinc (Zn) and includes an imidazolate ligand:

[0112] [Chemical Formula 2-2]

[0113]

[0114] In one embodiment, when the zeolite-mimicking metal-organic framework includes R2, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) may be 93° to 97°.

[0115] In the case of a zeolite-mimicking metal-organic framework comprising the above chemical formula 2-2, the OTO angle (depending on temperature change) The change is minimal.

[0116] A method for manufacturing a zeolite-mimicking metal-organic framework according to another embodiment of the present invention comprises the steps of: preparing a mixed solution by mixing a metal compound containing a metal ion, an imidazole, an amine, a hydroxyl-based additive, and a solvent; and manufacturing a metal-imidazole from the mixed solution through a solvothermal reaction.

[0117] The above mixed solution preparation step is a step of preparing a mixed solution by mixing a metal compound containing metal ions, an imidazole, an amine and a hydroxyl-based additive and a solvent.

[0118] The above metal ion may include at least one selected from the group consisting of zinc (Zn), cobalt (Co), iron (Fe), cadmium (Cd), copper (Cu), and manganese (Mn).

[0119] In one embodiment, the metal compound may comprise at least one selected from the group consisting of a zinc compound, a cobalt compound, an iron compound, a cadmium compound, a copper compound, and a manganese compound.

[0120] The above zinc compound is zinc trifluoro-methasulfonate , zinc nitrate (Zn(NO3)2), zinc acetate, ), zinc trifluoromethanesulfonate, zinc acetate, ), zinc chloride and zinc fluoride hydrate (ZnF2), zinc dichloride It may include at least one selected from a group consisting of

[0121] The above cobalt compound may comprise at least one selected from the group consisting of cobalt chloride (CoCl2), cobalt fluoride (CoF2), cobalt hydroxide (Co(OH)2) and cobalt sulfate (CoSO4).

[0122] The above iron compounds are iron sulfate (FeSO4), iron nitrate, It may include at least one selected from the group consisting of iron chloride (FeCl3), iron bromide (FeBr2, FeBr3), and iron hydroxide (Fe(OH)2).

[0123] The above cadmium compound may include at least one selected from the group consisting of cadmium fluoride (CdF2), cadmium chloride (CdCl2), cadmium bromide (CdBr2), cadmium iodide (CdI2), cadmium nitrate (Cd(NO3)2), and cadmium hydrate (Cd(OH)2).

[0124] The copper compound may comprise at least one selected from the group consisting of copper sulfide (CuS), copper sulfate (CuSO4), copper acetate (Cu(CO2CH3)2), copper chloride (CuCl2), copper iodide (CuI2), and copper hydroxide (Cu(OH)2).

[0125] The above manganese compound may include at least one selected from the group consisting of manganese sulfate (MnSO4), manganese chloride (MnCl2), and manganese nitrate (Mn(NO3)2).

[0126] The above metal compound may be in the form of a hydrate.

[0127] In one embodiment, amine and hydroxyl-based additives may be used during the solvothermal reaction.

[0128] In one embodiment, the amine and hydroxyl-based additives are triethylamine (TEA), benzylamine (BA), piperidine (PD), ethylenediamine (EDA), piperazine (PZ), benzene-1,4-diamine (BD), and alpha-cyclodextrin. , beta cyclodextrin , gamma cyclodextrin It may include at least one selected from a group consisting of

[0129] The above amide and pyrrolidine-based organic solvents contain NH2 and OH groups that can competitively bind to N of the imidazole used as a ligand of the zeolite-mimicking metal-organic framework according to one embodiment of the present invention, so that the reaction can be controlled.

[0130] Preferably, the amine and hydroxyl-based additives may be ethylenediamine (EDA).

[0131] In one embodiment, the solvent may include an amide and a pyrrolidine-based organic solvent.

[0132] In one embodiment, the amide and pyrrolidine-based organic solvent may comprise at least one selected from the group consisting of dimethylformamide (N,N-Dimethylformamide; DMF), diethylformamide (N,N-Diethylformamide; DEF), methylpyrrolidine (1-Methylpyrrolidine), dibutylformamide (N,N-Dibutylformamide; DBF), diethylbenzamide (N,N-Diethylbenzamide; DEB), diethylacetamide (N,N-diethylacetamide; DEA), methylformamide (N-methylformamide; NMF), and dimethylacetamide (N,N-dimethylacetamide; DMA).

[0133] Preferably, the amide and pyrrolidine-based organic solvent may include diethylformamide (N,N-diethylformamide; DEF), dimethylformamide (N,N-dimethylformamide; DMF), or both.

[0134] In one embodiment, the imidazole may comprise the following R1, R2, or both.

[0135] In one embodiment, the R1 may be selected from the following structures:

[0136]

[0137] In one embodiment, the R2 may be selected from the following structures:

[0138]

[0139] In one embodiment, the mixed solution may be a mixture of metal ions and imidazole in a molar ratio of 1:0.02 to 1:20.

[0140] Preferably, based on the crystal structure, the ratio of metal ions to imidazole may be 1:2.

[0141] If the above molar ratio is not satisfied, the yield may become very low due to the large concentration difference between the metal ions and the imidazole, or there is a possibility that the metal ions and the imidazole may recrystallize separately instead of reacting with each other.

[0142] In one embodiment, the solvothermal reaction comprises: 20 ℃ to 150 ℃; 20 ℃ to 130 ℃; 20 ℃ to 100 ℃; 20 ℃ to 80 ℃; 20 ℃ to 50 ℃; 30 ℃ to 150 ℃; 30 ℃ to 120 ℃; 30 ℃ to 100 ℃; 30 ℃ to 80 ℃; 30 ℃ to 60 ℃; 30 ℃ to 40 ℃; 50 ℃ to 150 ℃; 50 ℃ to 120 ℃; 50 ℃ to 100 ℃; 50 ℃ to 80 ℃; 50 ℃ to 60 ℃; 80 ℃ to 150 ℃; 80 ℃ to 120 ℃; Under temperature conditions of 80 ℃ to 100 ℃; 100 ℃ to 150 ℃; 100 ℃ to 120 ℃; 120 ℃ to 150 ℃; or 100 ℃ to 130 ℃, for 12 hours to 240 hours; 12 hours to 180 hours; 12 hours to 120 hours; 12 hours to 60 hours; 12 hours to 30 hours; 24 hours to 240 hours; 24 hours to 180 hours; 24 hours to 120 hours; 24 hours to 60 hours; 24 hours to 30 hours; 48 hours to 240 hours; 48 hours to 180 hours; 48 hours to 120 hours; 48 hours to 60 hours; 60 hours to 240 hours; 60 hours to 180 hours; It may be performed for 60 to 120 hours; 120 to 240 hours; or 120 to 180 hours.

[0143] At temperatures below room temperature, the energy required for crystal growth is insufficient for the above solvothermal reaction, so self-assembly occurs very slowly, and at temperatures above 150°C, the solvent used is close to its boiling point, so the solvent vaporizes, and there is a possibility that the normal reaction will not occur.

[0144] If the time of the above solvothermal reaction is less than 12 hours, the reaction may not proceed sufficiently, and the yield may be very low. If it exceeds 240 hours, the crystals already formed will not change even if the reaction conditions are maintained, so the maximum time is no longer meaningful as all reactants have reacted sufficiently.

[0145] The present invention will be explained in more detail below through examples and comparative examples.

[0146] However, the following examples are merely for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[0147] Machines have been continuously developed in response to the demands of everyday life and industrial applications. While the careful design of molecular-scale devices often exhibits enhanced properties along with mechanical motion, controlling dynamics within solid molecular structures remains a significant challenge. In the embodiments of the present invention, the unique mechanical properties of zeolitic imidazolate frameworks (ZIFs) containing hidden mechanical components were experimentally investigated. By combining experimental and theoretical approaches, the mechanical capabilities of ZIFs were discovered, in which connected composite building units operate similarly to mechanical connection systems. Importantly, the embodiments of the present invention suggest that specific ZIF subunits serve as core mechanical components, thereby presenting an innovative perspective on the future design of solid molecular machines.

[0148] [Example]

[0149] ingredient

[0150] Zinc trifluoromethanesulfonate (TCI), zinc nitrate hexahydrate (Sigma Aldrich), imidazole (Alfa), 5,6-dimethylbenzimidazole (Sigma Aldrich), dimethylformamide (Junsei), and diethylformamide (TCI) were used without further purification.

[0151] Synthesis of gis-ZIF-1

[0152] Zinc trifluoromethanesulfonate (2.908 g, 8 mmol) and imidazole (2.18 g, 32 mmol) were each dissolved in 40 mL of N,N-diethylformamide (DEF) solvent to prepare a stock solution. Then, 2 mL of the zinc trifluoromethanesulfonate stock solution and 1 mL of the imidazole stock solution were placed in a 10 mL vial. Subsequently, an additional 1 mL of DEF and 30 mL of ethylenediamine (0.45 mmol) The mixture was mixed in a 10 mL vial. The mixed solution was heated at 90 °C for 48 hours. After the reaction, colorless crystals were collected and washed with DEF.

[0153] Synthesis of gis-ZIF-2

[0154] Zinc nitrate hexahydrate (100 mg, 0.34 mmol), imidazole (65 mg, 0.95 mmol), and 5,6-dimethylbenzimidazole (77 mg, 0.53 mmol) were each dissolved in 5 mL of N,N-dimethylformamide (DMF) solvent to prepare stock solutions. Then, 1 mL of each stock solution was mixed into 5 mL vials (total solution of 3 mL per vial). The mixed solution was heated at 120 °C for 72 hours. After the reaction, brown crystals were collected and washed with DMF.

[0155] Synthetic and structural properties

[0156] FIG. 1 is a diagram showing the structural similarity between gis-ZIF-1 and zeolite according to an embodiment of the present invention, and FIG. 2 is a diagram showing a ball and rod model of the gis-ZIF-1 single crystal structure according to an embodiment of the present invention.

[0157] Referring to Figures 1 and 2, it was revealed through single-crystal X-ray diffraction (SCXRD) that gis-ZIF-1 is one of the Zn(Im)2 polymorphs having the gis topology. The gis topology is one of the zeolite topologies composed of one type of tetrahedral vertices and two types of edges, and the network includes two types of CBU, four-membered rings (4MR), and helical chains.

[0158] It was noted that gis-ZIF-1 is characterized by a unique structure unlike the previously reported ZIF-6. To explain in detail, ZIF-6 and gis-ZIF-1 have geometrically different CBUs, and Since it is a flattened square and butterfly tetrahedron, consequently, the difference in space groups of ZIF-6 (D4h) and gis-ZIF-1 of (C4h) occurs in each case. In particular, The space group has reflection symmetry removed, and 4MR has rotational degrees of freedom along 41 screw axes. It is a crystallographic subgroup of.

[0159] Within the unit cell, gis-ZIF-1 contains 16 Zn atoms interconnected by 32 Im linkers. All Zn atoms exhibit symmetry equivalence, and the Im linkers occupy two positions with the same symmetry. Specifically, one type of Im linker forms a 4MR, and the other type forms a helical chain.

[0160] These CBUs are linked via Zn atoms. Analysis using nuclear magnetic resonance (NMR) spectroscopy revealed the presence of DEF solvent within gis-ZIF-1 and the absence of EDA molecules. In particular, the tetragonal geometry of gis-ZIF-1 is significantly affected by the DEF solvent, as observed in the structural changes when the MeOH-limited DEF solvent is removed through a solvent exchange process.

[0161] Thermal reaction

[0162] Considering the topological significance, it was expected that gis-ZIF-1 would potentially exhibit flexible properties similar to gis-zeolite. To confirm this structural flexibility, a temperature-dependent synchrotron SCXRD analysis was performed covering temperatures from 100 K to 350 K.

[0163] Figure 3 shows the relative change of parameters a and c according to temperature of gis-ZIF-1 according to an embodiment of the present invention.

[0164] Referring to Fig. 3, as the temperature increases, gis-ZIF-1 Anisotropic thermal expansion along the a and b axes was exhibited while maintaining the space group and gis phase. In the embodiment of the present invention, parameters a and b increased by 2.0%, while parameter c showed a change of 0.2%.

[0165] Figure 4 shows the relative change in the volume of a unit cell according to the temperature of gis-ZIF-1 according to an embodiment of the present invention.

[0166] Referring to Figure 4, the volume of the unit cell increased by 4.4% from 100 K to 350 K and by 7.6% from 200 K to 350 K.

[0167] This thermal expansion occurred particularly at 200 K, and non-linear expansion similar to the guest-induced thermal expansion observed in MOFs was observed. Accordingly, the coefficient of thermal expansion was calculated from changes in cell parameters and cell volume. According to calculations, for gis-ZIF-1, the parameter value at 200 K is up to 690.7 × 10⁻⁶. -6 K -1 and the cell volume is 1709.7×10 -6 K -1 It exhibited tremendous thermal expansion. It is worth noting that the thermal expansion anisotropy observed in flexible materials arises from the molecular basis of the expansion. Therefore, we initiated a detailed exploration of the gis-ZIF-1 structure to identify the precise molecular motions contributing to this anisotropic thermal expansion.

[0168] For a detailed analysis of the thermal response, the structure was simplified using a zeolite TO2 model in which the T and O sites represent the centers of the Zn atom and the Im linker, respectively. This model incorporates three variables: TO length, TOT, and OTO angles. Within the zeolite model of gis-ZIF-1, the asymmetric unit is a TO2 with one type of T center and two types of O bridges, represented as T4O4 for 4MR and T for the helical chain. n O nIt corresponds to. By tracking the distance between TO tetrahedrons, called the TT length, it was found that there are two types of symmetrically identical TT lengths, which differ depending on the type of O bridge involved. The variation in TT length over the temperature range was negligible, and for each type, 6.02(2) and 5.93(2) It was measured as such. Afterwards, these TT lengths were analyzed along three axes parallel to the unit cell.

[0169] FIG. 5 is a diagram comparing the length change inside the rigid mechanical components of gis-ZIF-1 according to an embodiment of the present invention and the angle between these components.

[0170] Referring to Fig. 5, L1 and L2 are indicated in the ab plane and L3 is indicated along the c axis. These lengths were substantially constant in the SCXRD data and showed a variation of less than 2%.

[0171] FIG. 6 is a diagram showing a CBU as a mechanical component inside the gis topology of the gis-ZIF-1 structure according to an embodiment of the present invention.

[0172] Referring to Fig. 6, the green component represents a 4-membered ring (4MR), and the copper component represents a helical chain with 41 screw symmetries. This clearly demonstrates the stiffness of the CBU functioning as a mechanical component. Furthermore, identifying these stiffness components highlights important factors.

[0173] Figure 7 shows the mechanical movement of the ZIF machine in the gis-ZIF-1 structure according to an embodiment of the present invention, and the SCXRD analysis according to temperature. This is a diagram showing the change of.

[0174] Referring to Fig. 7, the rotation angle, which is the angle between 4MR and the helical chain ( ) changes by about 9° over the temperature range. This kind of kinetics was also observed in DMA-exchanged gis-ZIF-1, and The angle was changed by 10°. This selective flexibility was very similar to the mechanical connection behavior of existing machines. Therefore, gis-ZIF-1 exhibited machine-like operation in response to temperature changes. This allowed for a detailed exploration of the dynamics of gis-ZIF-1.

[0175] Mathematical analysis has consistently been effective in solving the dynamics of various mechanical systems. The mechanical behavior of gis-ZIF-1 is primarily a single variable It can be thoroughly explained through a mathematical model defined as.

[0176] FIG. 8 is a 2D projection model of gis-ZIF-1 according to an embodiment of the present invention and FIG. 9 is This is a diagram showing the mathematical analysis of ZIF dynamics through a comparison of the experimental and calculated relationships between the parameters.

[0177] As shown in Fig. 8, a single variable It is directly linked to Cartesian coordinates derived from the projection onto the ab plane within the unit cell of gis-ZIF-1. Consequently, the parameters and The correlation between them can be expressed by the simple [Equation 1] as defined below:

[0178] [Mathematical Formula 1]

[0179]

[0180] In Equation 1, the change in parameters is without the involvement of additional variables. It is directly correlated with changes and was confirmed in SCXRD data that varies with temperature under the assumption that L1 and L2 are kept constant.

[0181] Designated to verify the validity of this equation The parameters calculated within the range were compared with the crystallographic data (Fig. 9). As shown in Fig. 9, the parameters and The relationship between them matched the calculated values ​​derived from the mathematical equation very well. It was noted that this ZIF dynamic exhibits a rotational correlation transformation form similar to the slider-crank mechanism observed in general and biological machines. Additionally, a macroscopic version of gis-ZIF-1 with the same dynamics was demonstrated using this mathematical equation and 3D printing technology.

[0182] To investigate the molecular origin of this dynamic, the mechanical model of gis-ZIF-1 was directly compared with the zeolite TO2 model. Based on the asymmetric unit TO2, the unit cell of gis-ZIF-1 contains four symmetrically distinct TO lengths. These values ​​remained nearly constant regardless of temperature. Two TOT angles, also known as bridging angles, were unique within the unit cell, each associated with the symmetry of the O sites. Each TOT angle corresponds to a specific mechanical component, the 4MR and the helical chain, respectively. The TOT angle changed by less than 1° within the 4MR component, but changed to 2.9° within the helical chain as the temperature increased.

[0183] However, the OTO angle, also known as the tetrahedral angle, represents the angle between 4MR and the helical chain and generates six symmetrically independent OTO angles. Among these, we focused on two angles perpendicular to each other within the TO4 tetrahedron. One of these angles increased by approximately 3.6°, while the other decreased by approximately 3.2°. The remaining four OTO angles remained rigid.

[0184] FIG. 10 shows the rotation angle as a function of temperature of gis-ZIF-1 according to an embodiment of the present invention. and OTO angle This is a diagram showing a comparison of

[0185] Referring to Fig. 10, as the temperature increases, there are two types of angles ( and ) increased. Increased OTO angle( The position of ) is the rotation angle( It exactly coincided with the position of ), and the change showed a similar trend. This suggests that the molecular origin of this mechanical behavior is the OTO angle Indicates that it is in a selective variation of.

[0186] FIG. 11 shows the rotation angle of gis-ZIF-1 and gis-zeolite according to an embodiment of the present invention. and OTO angle This is a diagram comparing mechanics from the side.

[0187] Referring to Fig. 11, in the case of gis-zeolite, the OTO angle is stiffer than the TOT angle under mechanical stimulation, so a constant rotation angle Another mechanism having occurs.

[0188] Replacement of mechanical components

[0189] Additional mechanical aspects within gis-ZIF-1 were further explored by replacing mechanical components with bulky functional groups.

[0190] FIG. 12 is a diagram showing gis-ZIF-2 with adjusted mechanical components by attaching functional groups to gis-ZIF-1 molecular links according to an embodiment of the present invention.

[0191] The candidate of selection, gis-ZIF-2, is isostructured with TIF-5 and belongs to the gis-type ZIF. ZIFs include 5,6-dimethylbenzimidazolate (dmbIm), a bulky imidazolate with a helical chain. The synthesis of gis-ZIF-2 Solventothermal reactions utilizing Im and dmbIm were included, and the crystal structures were confirmed via synchrotron SCXRD. Notably, gis-ZIF-2 is identical to gis-ZIF-1 It is crystallized in a gis topology with a space group. The Im and dmbIm portions are distinctly separated within the crystal structure, with Im constituting the 4MR component and dmbIm forming the helical chain component. NMR spectroscopy confirmed the ratio of Im to dmbIm to be 1:1, which is consistent with the crystallographic ratio of the 4MR and helical chain components. Within the unit cell, gis-ZIF-2 contains 16 Zn atoms interconnected by 16 Im linkers and 16 dmbIm linkers. Zn, Im, and dmbIm each occupy a single symmetry position.

[0192] The thermal response of gis-ZIF-2 was explored through temperature-dependent synchrotron SCXRD analysis within a temperature range of 100 K to 350 K.

[0193] FIG. 13 is a diagram showing the extended structure of gis-ZIF-1 (left) and gis-ZIF-2 (right) at 100 K according to an embodiment of the present invention.

[0194] Referring to Fig. 13, the calculated coefficient of thermal expansion confirmed that the thermal expansion of gis-ZIF-2 is significantly limited due to the presence of bulky components, and for the parameter, the maximum value is And in the case of cell volume and was observed at 200 K. Similar to gis-ZIF-1, gis-ZIF-2 also 0.1 over the entire temperature range. Maintains rigid components with minimal change. Rotation angle It increased by 1.4°, which indicates that rotational dynamics are disrupted due to the replacement of mechanical components.

[0195] FIG. 14 shows the rotation angles of gis-ZIF-1 and gis-ZIF-2 according to an embodiment of the present invention. and OTO angle This is a diagram showing the correlation between the SCXRD data. The range is represented by a color space (orange: gis-ZIF-1, green: gis-ZIF-2).

[0196] Referring to Fig. 14, the OTO angle in terms of molecular origin It increased by about 1.7°, which is about half the increase observed in gis-ZIF-1.

[0197] Rotation angle to reveal these controllable dynamics The potential energy profile of the gis-ZIF series was calculated by varying it.

[0198] Figure 15 is a diagram comparing the relative potential energy profiles per Zn for simulated ZIF dynamics.

[0199] Referring to Fig. 15, the simulated energy curves clearly show the difference between gis-ZIF-1 and gis-ZIF-2. The shallow curve observed in gis-ZIF-1 indicates the ease of rotational dynamics, whereas the steep curve in gis-ZIF-2 shows the disturbance of dynamics.

[0200] mechanical properties

[0201] So far, the mechanical performance of gis-ZIF-1 has been demonstrated based on thermal response. Therefore, mechanical properties were investigated through theoretical calculations. The obtained elastic properties include the elastic modulus (E) calculated from the elastic constant using ElaStic software, and linear compressibility. , shear modulus (G), Poisson's ratio am.

[0202] FIG. 16 is a 3D surface and 2D polar plot of Young's modulus, linear compressibility, maximum (orange) and minimum (green) shear modulus, and Poisson's ratio of gis-ZIF-1 according to an embodiment of the present invention. Each direction (x, y, z) represents the a, b, and c parameter directions in the orthorhombic system of gis-ZIF-1.

[0203] Referring to Fig. 16, the minimum value for the elastic modulus of gis-ZIF-1 is 0.84 GPa, where strain occurs along the c-axis, and the maximum value is 1.60 GPa, where the strain axis is perpendicular to the c-axis. The elastic modulus indicates compressive elasticity; that is, compression of the gis-ZIF-1 structure is preferred to be perpendicular to the c-axis, and the anisotropy is approximately 1.89 is. Linear compressibility shows a trend similar to the elastic modulus, and the anisotropy is approximately 4.10 These anisotropic mechanical properties are in good agreement with anisotropic thermal response and related ZIF kinetics.

[0204] FIG. 17 is a figure showing the relationship between the maximum Young's modulus and the shear modulus of gis-ZIF-1, ZIF, and carboxylate-based MOF according to an embodiment of the present invention.

[0205] Referring to Fig. 17, the shear modulus The minimum value of is 0.29, and the maximum value It is 0.61. gis-ZIF-1 is and It ranks lowest in terms of value, and when compared to other MOFs It ranks highest in terms of aspect.

[0206] conclusion

[0207] In summary, embodiments of the present invention present gis-ZIF-1, which utilizes composite building units (CBUs) as mechanical components to implement mechanical behavior similar to a slider-crank mechanism. Unlike conventional zeolite and Cu-based ZIFs, this system exhibits flexible mechanical behavior based on molecular movement and can precisely model behavior similar to macro-machines through mathematical modeling. In particular, when bulky chemical functional groups are introduced into the ZIF structure in embodiments of the present invention, these functional groups act as stoppers similar to those of macro-machines, thereby exhibiting unique mechanical properties. Furthermore, gis-ZIF-1 exhibits low Young's modulus and shear modulus, making it a potential candidate for applications requiring energy absorption.

[0208] Embodiments of the present invention demonstrate that ZIF nanomachines function as mechanical metamaterials, where their mechanical properties are determined primarily by the structure and connectivity of rigid components. These ZIF nanomachines can generate efficient synergy between rigid components through tunable chemical functions. Such capabilities open the way for the advancement of properties linked to mechanical behavior, demonstrating significant potential in nanotechnology fields including soft robotics and digital data storage. These efforts are expected to provide a blueprint for designing solid-state nanomachines at the molecular scale.

[0209] Although the embodiments have been described above with reference to the limited drawings, those skilled in the art can apply various technical modifications and variations based on the above. For example, suitable results may be achieved even if the described techniques are performed in a different order than described, and / or if the components of the described system, structure, device, circuit, etc. are combined or assembled in a form different from described, or replaced or substituted by other components or equivalents.

[0210] Therefore, other implementations, other embodiments, and equivalents to the claims also fall within the scope of the claims set forth below.

Claims

1. Zeolite-mimicking metal-organic framework comprising the following chemical formula 1: [Chemical Formula 1] The above M is a central metal, and The above R comprises R1, R2, or both containing an imidazole group.

2. Zeolite-mimicking metal-organic framework comprising the following chemical formula 2: [Chemical Formula 2] The above M is a central metal, and The above R comprises R1, R2, or both containing an imidazole group.

3. In Paragraph 1 or 2, The above central metal comprises at least one selected from the group consisting of zinc (Zn), cobalt (Co), iron (Fe), cadmium (Cd), copper (Cu), and manganese (Mn). Zeolite-mimicking metal-organic framework.

4. In Paragraph 1 or 2, The above R1 is selected from the following structure, Zeolite-mimicking metal-organic framework.

5. In Paragraph 1 or 2, The above R2 is selected from the following structure, Zeolite-mimicking metal-organic framework.

6. In Paragraph 1 or 2, When R1 is included in the above zeolite-mimicking metal-organic framework, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) is 100° to 105°, and When R2 is included in the above zeolite-mimicking metal-organic framework, the rotation angle ( As ) increases from 60° to 75°, the OTO angle ( ) is 93° to 97°, Zeolite-mimicking metal-organic framework.

7. A step of preparing a mixed solution by mixing a metal compound containing metal ions, an imidazole, an amine and a hydroxyl-based additive and a solvent; and A step of preparing a metal-imidazole from the above mixed solution through a solvothermal reaction; including, Method for manufacturing a zeolite-mimicking metal-organic framework.

8. In Paragraph 7, The above metal compound comprises at least one selected from the group consisting of zinc compounds, cobalt compounds, iron compounds, cadmium compounds, copper compounds, and manganese compounds, and The above zinc compound is zinc trifluoro-methasulfonate , zinc nitrate (Zn(NO3)2), zinc acetate (Zinc acetate, , zinc trifluoromethanesulfonate, zinc acetate, Zinc chloride and zinc fluoride hydrate (ZnF2), zinc dichloride It includes at least one selected from a group consisting of, and The above cobalt compound comprises at least one selected from the group consisting of cobalt chloride (CoCl2), cobalt fluoride (CoF2), cobalt hydroxide (Co(OH)2), and cobalt sulfate (CoSO4). The above iron compounds are iron sulfate (FeSO4), iron nitrate, It comprises at least one selected from the group consisting of iron chloride (FeCl3), iron bromide (FeBr2, FeBr3), and iron hydroxide (Fe(OH)2), and The above cadmium compound comprises at least one selected from the group consisting of cadmium fluoride (CdF2), cadmium chloride (CdCl2), cadmium bromide (CdBr2), cadmium iodide (CdI2), cadmium nitrate (Cd(NO3)2), and cadmium hydrate (Cd(OH)2). The copper compound comprises at least one selected from the group consisting of copper sulfide (CuS), copper sulfate (CuSO4), copper acetate (Cu(CO2CH3)2), copper chloride (CuCl2), copper iodide (CuI2), and copper hydroxide (Cu(OH)2). The above manganese compound comprises at least one selected from the group consisting of manganese sulfate (MnSO4), manganese chloride (MnCl2), and manganese nitrate (Mn(NO3)2). Method for manufacturing a zeolite-mimicking metal-organic framework.

9. In Paragraph 7, The above solvothermal reaction utilizes amine and hydroxyl-based additives, and The above amine and hydroxyl-based additives are triethylamine (TEA), benzylamine (BA), piperidine (PD), ethylenediamine (EDA), piperazine (PZ), benzene-1,4-diamine (BD), and alpha-cyclodextrin. , beta cyclodextrin , gamma cyclodextrin Comprising at least one selected from a group consisting of, Method for manufacturing a zeolite-mimicking metal-organic framework.

10. In Paragraph 7, The above solvent includes amide and pyrrolidine-based organic solvents, and The above amide and pyrrolidine-based organic solvent comprises at least one selected from the group consisting of dimethylformamide (N,N-Dimethylformamide; DMF), diethylformamide (N,N-Diethylformamide; DEF), methylpyrrolidine (1-Methylpyrrolidine), dibutylformamide (N,N-Dibutylformamide; DBF), diethylbenzamide (N,N-Diethylbenzamide; DEB), diethylacetamide (N,N-diethylacetamide; DEA), methylformamide (N-methylformamide; NMF), and dimethylacetamide (N,N-dimethylacetamide; DMA). Method for manufacturing a zeolite-mimicking metal-organic framework.

11. In Paragraph 7, The above imidazole comprises the following R1, R2, or both, and The above R1 is selected from the following structure, and The above R2 is selected from the following structure, Method for manufacturing a zeolite-mimicking metal-organic framework.

12. In Paragraph 7, The above mixed solution is prepared by mixing metal ions and imidazole in a molar ratio of 1:0.02 to 1:

20. Method for manufacturing a zeolite-mimicking metal-organic framework.

13. In Paragraph 7, The above solvothermal reaction is carried out for 12 to 240 hours at a temperature of 20 ℃ to 150 ℃, Method for manufacturing a zeolite-mimicking metal-organic framework.

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