KR20200047352A - Nanoparticle comprising modulated zeolitic imidazolate framework and method of preparing the same - Google Patents

Abstract

The present invention relates to a nanoparticle comprising a crystal structure-controlled zeolitic imidazolate framework and a method for manufacturing the same. The nanoparticle according to the present invention includes a metal ion, and an organic ligand bound to the metal ion, wherein the organic ligand includes an imidazolate-based organic ligand and an alkyl amine-based organic ligand.

Description

Nanoparticles containing a zeolite imidazolate-based structure with controlled crystal structure and a method for manufacturing the same

The present invention relates to a method for producing nanoparticles and nanoparticles comprising a zeolitic imidazolate framework (ZIF) and having a controlled crystal structure.

Metal organic frameworks (MOFs) are relatively new hybrid organic-inorganic materials, which are microporous crystal materials composed of metal atoms or metal clusters and organic ligands that connect them to coordinate bonds.

The pore size and physical / chemical properties of the MOF can be controlled by the selection of appropriate metal atoms and organic ligands.

In addition, through additional chemical reaction to MOF, hybrid-type MOF synthesis is possible by substituting metal atoms and organic ligands, which are components of MOF, with other metal atoms and organic ligands, and depending on the degree of substitution, pore size and physical / chemical Further control of properties is possible. Because of this particular nature of MOF, it has been shown to have potential for gas storage and / or absorption, catalysis, and potential application as a separator.

In particular, zeolitic imidazolate frameworks (ZIF), as a sub-concept of metalorganic structures, consist of a metal node (generally zinc or cobalt) connected to an imidazolate (or imidazolate derivative) ligand. .

US9527872 B2

An object of the present application is to provide a nanoparticle capable of controlling crystal structure by using an imidazolate organic ligand and a non-imidazolate organic ligand as organic ligands.

Another object of the present application is to provide nanoparticles having high dispersion and high concentration dispersion characteristics that are well dispersed in an organic solvent or a polymer matrix through a combination of an imidazolate-based organic ligand and a non-imidazolate-based organic ligand.

Another object of the present application is to provide nanoparticles having a size of 100 nm or less or 50 nm or less and having excellent compatibility with a polymer matrix.

Another object of the present application is to provide a method for manufacturing a high-quality and high-mass synthesis of the nanoparticles.

However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

The object of the present invention is a nanoparticle including a zeolitic imidazolate framework (ZIF), comprising: a metal ion; It includes an organic ligand bound to the metal ion, and the organic ligand is achieved by including an imidazolate-based organic ligand and an alkyl amine-based organic ligand.

At least one of the spacing of the crystal planes, the distribution of the crystal planes, and the bonding strength may be adjusted according to the use ratio of the alkylamine-based organic ligand.

The alkyl amine-based organic ligand may be directly bonded to the metal ion.

The alkyl amine-based organic ligand includes at least one of primary, secondary, and tertiary amines, and includes methyl, ethyl, propyl, butyl, pentyl, hexyl, epsil, octyl, nonyl, decyl, undecyl, and dode It can be selected from the group of alkyl amines having an alkyl chain of any one of: seal, propadecyl, butadecyl, pentadecyl, hexadecyl, eptadecyl, octadecyl and nodadecyl.

The ratio of the organic ligand to the imidazolate-based organic ligand to the alkyl amine-based organic ligand may be 99.9% by weight: 0.1% by weight to 80% by weight to 20% by weight.

When the metal ion is cobalt, the spacing of the (011) crystal surface of the AZIF nanoparticles is 11.9Å to 12.15Å, and when the metal ion is zinc, the spacing of the (011) crystal surface of the AZIF nanoparticles is 12.0Å to 12.25Å Can be

The nanoparticles may have a size of 100 nm or less.

The nanoparticles may have a size of 50 nm or less.

The nanoparticles may be dispersed in an amphiphilic solvent.

The nanoparticles can be dispersed in an amphiphilic solvent to a concentration of about 110 mg / mL.

The pores of the nanoparticles may be 0.1nm to 1nm.

The nanoparticles may be dispersed in a polymer matrix by 20% to 60% by weight to manufacture a hybrid membrane.

The nanoparticles may exhibit a mass loss of about 3% or less within 400 ° C in a TGA experiment.

When the metal ion is cobalt, the IR peak of Co-N of the AZIF nanoparticle increases by 1 to 3 cm ^-1 by the alkylamine-based organic ligand, and when the metal ion is zinc, Zn- of the AZIF nanoparticle The IR peak of N can be increased by 1.5 to 4 cm ^-1 by the alkylamine-based organic ligand.

The object of the present invention is a metal precursor, a precursor comprising an imidazole-based ligand compound and a first polar solvent in a method for preparing nanoparticles comprising a zeolite imidazolate-based structure (alkyl amine-zeolitic imidazolate framework, AZIF) Heating the solution under stirring; Adding an organic base solution to the precursor solution to obtain a suspension comprising micro-sized chunks comprising the zeolite imidazolate-based structure; Diluting the suspension by adding a second polar solvent to the suspension; And obtaining nanoparticles comprising the zeolite imidazolate-based structure from the diluted suspension. It is achieved by including.

The metal precursors are Co, Zn, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, Acetate salts of one or more metals selected from the group consisting of W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg and Uub .

The imidazole-based ligand compound may include one or more selected from imidazole-based compounds represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

;

;

[Formula 2]

;

;

In each of Formula 1 and Formula 2,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently H, C1 to C10 alkyl group, halogen, hydroxy, cyano, nitro or aldehyde group,

A ¹ , A ² , A ³ , and A ⁴ are each independently C or N,

However, R ⁵ , R ⁶ , R ⁷ , and R ⁸ exist only when A ¹ and A ⁴ are C.

The first polar solvent and the second polar solvent are each independently alcohol, methanol, ethanol, propanol, ethylene glycol, water, dimethylformamide, dimethyl sulfoxide, acetonitrile, and dimethylacetamide. It may include one or more selected from the group consisting of.

The pH of the second polar solvent may be higher than 5.

Heating of the precursor solution may be performed isothermally.

The organic base solution includes an alkyl amine-based organic ligand, and the alkyl amine-based organic ligand includes at least one of primary, secondary, and tertiary amines, and includes methyl, ethyl, propyl, butyl, and pentyl, Alkyl amines having an alkyl chain of any of hexyl, epsil, octyl, nonyl, decyl, undecyl, dodecyl, propadecyl, butadecyl, pentadecyl, hexadecyl, eptadecyl, octadecyl and nodadecyl It may include one or more selected from the group.

The pKa of the organic base solution may be higher than 7.

According to the present application, a nanoparticle having a zeolite imidazolate-based structure, a crystal structure being controlled, and simultaneously comprising an imidazolate-based organic ligand and a non-imidazolate-based alkyl amine-based organic ligand is provided. The nanoparticles have the advantage of being well dispersed at high concentrations in a solvent or a polymer material, and also have high dispersion stability in a solvent, which is suitable for processes requiring high dispersion properties. Nanoparticles are capable of uniform and high concentration dispersion in the polymer even when complexed with a polymer material, greatly improving the amount of nanoparticles that can be introduced into the organic-inorganic composite film compared to nanoparticles containing the previously reported zeolite imidazolate structure. It has the advantage that it is possible to uniformly disperse high concentrations in various polymer matrices. In addition, it has high interfacial adhesion properties with polymeric materials when compared to nanoparticles having a zeolite imidazolate-based structure as previously reported. The nanoparticles developed herein have the advantage of minimizing the phenomenon of unreacted organic ligands remaining in the nanoparticles having a high purity material and having a zeolite imidazolate structure, and the size of nanoparticles having a zeolite imidazolate structure. It can be synthesized below 100nm or 50nm, making it possible to manufacture thin films in complex with polymer materials.

The method for preparing nanoparticles according to an embodiment of the present application can synthesize nanoparticles in a large amount of time in a short time, and specifically, has a merit that the reaction time is short and recovery of the product can be performed simply and quickly.

1, in the embodiment of the present application, the synthesis process of AZIF-67 particles is expressed as a change in reaction temperature over time, and at this time, the color of the solution in each step and the size change of the particles at this time are dynamic light scattering (dynamic light scattering, DLS) It is a graph showing the results of analysis by spectroscopy.
2 is a basic structural formula that can be shown when AZIF-67 nanoparticles are synthesized using various alkylamines.
Figure 3, in the embodiment of the present application, the structure of the nanoparticles and the structure of the rombic octahedron and (110) and (200) shows the crystal plane and the spacing between the crystal planes and the reaction solution when synthesizing AZIF-67 nanoparticles It is an XRD graph of the AZIF-67 nanoparticles obtained according to the amount of Bu3N introduced into.
4 is an XRD graph of AZIF-67 incorporating various alkylamines synthesized according to the examples herein.
5 is an XRD graph of AZIF-8 synthesized according to the Examples herein.
FIG. 6 is an SEM image of ZIF-67 nanoparticles and general ZIF-67 nanoparticles incorporating various alkylamines synthesized according to the examples herein.
7 is, in the embodiment of the present application, AZIF-8-Bu ₃ N5 and ZIF-8 in general and AZIF-67-Bu ₃ N5 and ZIF-67 in general according to the concentration of each sample in NMP solvent over time This is a photograph showing the degree of dispersion.
FIG. 8 is a photograph showing dispersion stability after 3 days after dispersing AZIF-67-Bu ₃ N5 and general ZIF-67 according to concentrations in an NMP solvent in an embodiment of the present application.
9 is a hybrid membrane photograph prepared when the AZIF-67 and the general ZIF-67 nanoparticles are dispersed at a high concentration in the 6FDA-DAM polyimide (PI) polymer in the embodiment of the present application.
FIG. 10 is a photograph of a hybrid membrane prepared by dispersing AZIF-67 and AZIF-8 nanoparticles at high concentrations in various polymers including PSF and PI-based polymers.
11 is, in the embodiment of the present application, cross-section of a hybrid membrane prepared by dispersing AZIF-67 nanoparticles in various polymer materials through SEM images.
12 is, in the examples of the present application, the results of TGA analysis of AZIF-67 nanoparticles and AZIF-8 with various alkylamines introduced.
13 is, in the embodiment of the present application, when an alkylamine group is introduced into an AZIF-67 reaction solution, particles are aggregated into chunks, and an image is analyzed using a scanning electron microscope (SEM).
FIG. 14 is a ¹ H NMR spectra obtained by decomposing AZIF-67 nanoparticles in which various amounts and types of butylamine synthesized according to the examples of the present application are introduced with an acid.
FIG. 15 is a photograph of AZIF-67-Bu ₃ N5 nanoparticles obtained at one time through a large-scale reaction in the examples of the present application.
FIG. 16 is a ¹ H NMR spectra obtained by decomposing AZIF-67 nanoparticles obtained according to the amount of tributylamine introduced into the reaction in the synthesis of AZIF-67 nanoparticles in the Examples herein.
FIG. 17 is a ¹ H NMR spectra obtained by decomposing AZIF-8-Bu ₃ N5 nanoparticles with an acid in Examples herein.
FIG. 18 is a BET isothermal graph of AZIF-67 and AZIF-8 nanoparticles in the Examples herein.
FIG. 19 is an FT-IR graph analyzing the ionic bond strength between metals and organic ligands of AZIF-8 and AZIF-67 in the examples of the present application.

Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice. However, the present application may be implemented in various different forms and is not limited to the embodiments and examples described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout this specification, when a part is "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member in between. do.

Throughout this specification, when a member is said to be "on" another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated to the contrary.

As used herein, the terms “about”, “substantially”, and the like are used in or near the numerical values when manufacturing and substance tolerances unique to the stated meanings are presented, to aid understanding of the present application The exact or absolute value of the hazard is used to prevent unscrupulous use of the disclosed disclosure by unconscientious intruders.

The term “step of ~” or “step of ~” as used in the present specification does not mean “step for”.

Throughout the present specification, the term “combination (s)” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

Throughout the present specification, “nanoparticles comprising a zeolite imidazolate-based structure” may be abbreviated as “nanoparticles having a ZIF structure” or “ZIF nanoparticles”. In addition, "controlled nanoparticles in the crystal structure while simultaneously including a zeolite imidazolate-based structure and an imidazolate-based organic ligand and a heterogeneous non-imidazolate-based alkyl amine-based organic ligand" have a "AZIF structure." "Nanoparticles", "AZIF nanoparticles" or, in some cases, "nanoparticles".

In the present specification, ZIF-67 and AZIF-67 represent a case where the metal ion is cobalt, and ZIF-8 and AZIF-8 represent a case where the metal ion is zinc. For example, AZIF-67-Bu3N5 represents AZIF nanoparticles in which metal ions are cobalt prepared by adding tertiary butyl amine as an alkylamine at a 5 times molar ratio of metal ion precursors. Other AZIF nanoparticle markings can be understood through the examples above.

Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings. However, the present application is not limited to these embodiments and examples and drawings.

AZIF nanoparticles comprising an imidazolate-based organic ligand comprising a zeolite imidazolate-based structure and a heterologous non-imidazolate-based alkyl amine-based organic ligand simultaneously according to an embodiment of the present application, are heterogeneous non-imidazoles Ethyl amine, propyl amine, butyl amine, di ethyl amine, di propyl amine, di butyl amine, di ethyl amine, tri propyl amine, tri butyl amine, etc. may be included in the acrylate-based alkyl amine type, but is not limited thereto.

In one embodiment of the present application, the alkyl amine comprises primary, secondary and / or tertiary amines and alkyl chains in various lengths (FIG. 2). For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, epsil, octyl, nonyl, decyl, undecyl, dodecyl, propadecyl, butadecyl, pentadecyl, hexadecyl, eptadecyl, octadecyl, noda One or more of decyl may be used, but is not limited thereto.

In one embodiment of the present application, the ratio of the imidazolate-based organic ligand and the alkylamine-based organic ligand in the AZIF nanoparticles may be 99.9% by weight: 0.1% by weight to 80% by weight: 20% by weight (Table 1). .

In one embodiment of the present application, the spacing between crystal planes in the crystal structure of AZIF nanoparticles is reduced compared to ZIF nanoparticles. More specifically, when compared to the ZIF-67 nanoparticles in the (011) crystal plane of the AZIF-67 nanoparticles, the inter-planar spacing was reduced by (0.2) from 12.30 최대 to 12.15 최대 (D) from 12.30 최대 to maximum. 3), the interval can be adjusted according to the degree to which tributylamine is introduced. However, the molar ratio of tributylamine introduced during synthesis is reduced from 5 or more to the maximum, and even when introduced, the spacing between crystal planes is no longer changed. The change between crystal planes can be changed by chemical bond strength between metal ions and organic ligands, interaction energy between organic ligands, and gradient change due to the size of organic ligands, and mechanical bond strength between binding materials, which are properties inherent to specific materials. Will be affected. When a second organic ligand is introduced, the change in crystal structure and properties eventually affects the pore structure of AZIF nanoparticles. However, the change in the spacing between the crystal planes does not directly give a specific tendency to the change in the pore structure of the AZIF nanoparticles, and the chemical mechanical bond strength of the aforementioned metal ion and organic ligand and the interaction energy and space of the organic ligand The pore structure and its size may vary depending on the degree of inclination under the conditions.

In AZIF-67, the spacing of the (011) crystal surface of the AZIF nanoparticles may be 11.9 Å to 12.15 ,, and the spacing of the (011) crystal surface of the AZIF nanoparticles in AZIF-8 may be 12.0 Å to 12.25 Å.

In an embodiment of the present application, when an excess amount of tributylamine is introduced during synthesis, the crystal planes (022) and (112) crystal planes grow larger than those of the crystal planes (FIG. 3). In addition, when the molar ratio of tributylamine compared to the metal precursor is 2 to 5, the ratio of each crystal plane is similar, but when the molar ratio is 10, (022) and (112) crystal planes grow larger than the plane (FIG. 3). This phenomenon occurs when the growth of AZIF-67 nanoparticles increases the phase of the alkylamine in solution as much as methanol, whereby the growth of AZIF-67 nanoparticles is due to maximization of interaction with the crystal plane (022) and (112) crystal plane You can grow more dominant in. This tendency is that the (002) and (112) planes grow significantly despite the use of a 5 molar ratio compared to the metal precursor when trihexylamine having low compatibility with methanol is used as a second organic ligand in one embodiment herein. It can be confirmed by doing (Fig. 4). On the other hand, when triethylamine and tripropylamine, which have good compatibility with methanol solvents such as tributylamine, are used, the tendency is similar to that of tributylamine.

In one embodiment of the present application, the crystal structure of the AZIF-8 nanoparticles showed a change in crystal properties with a similar trend to that of the AZIF-67 nanoparticles compared to the general ZIF-8 nanoparticles (FIG. 5).

In one embodiment of the present application, the size of the nanoparticles may be 100 nm or less, and may be 5 nm to 100 nm or 5 nm to 50 nm (FIGS. 1 and 6), but is not limited thereto. The size of the nanoparticles may vary depending on the type of the metal precursor, but may be less than or equal to 100 nm, which is suitable for manufacturing a mixed matrix membrane (MMM), but can exhibit high gas separation performance. In general, the smaller the particle size, the higher the specific surface area in contact with the polymer, which contributes to improving the compatibility with the polymer. For example, the size of the nanoparticles is about 100 nm or less, about 80 nm or less, about 60 nm or less, about 50 nm or less, about 40 nm or less, about 30 nm or less, about 20 nm or less, about 10 nm or less, It may be about 1 nm to about 100 nm, about 5 nm to about 50 nm, or about 10 nm to about 30 nm, but is not limited thereto.

In one embodiment of the present application, the nanoparticles may have improved dispersibility in organic solvents, particularly amphiphilic solvents (FIG. 7). The organic solvent may be an amphiphilic solvent such as N-methyl pyrrolidone (NMP), dimethylformamide (DMF), but is not limited thereto.

In one embodiment of the present application, AZIF-67 and AZIF-8 nanoparticles may be dispersed to a concentration of about 110 mg / mL with respect to the organic solvent (FIG. 7), but are not limited thereto. For example, the dispersion concentration of the nanoparticles in the organic solvent is about 10 mg / mL to about 110 mg / mL, about 10 mg / mL to about 90 mg / mL, about 10 mg / mL to about 70 mg / mL, about 10 mg / mL to about 50 mg / mL, about 10 mg / mL to about 30 mg / mL, about 10 mg / mL to about 20 mg / mL, about 20 mg / mL to about 100 mg / mL, About 20 mg / mL to about 80 mg / mL, about 20 mg / mL to about 60 mg / mL, about 20 mg / mL to about 40 mg / mL, about 30 mg / mL to about 100 mg / mL, about 30 mg / mL to about 80 mg / mL, about 30 mg / mL to about 60 mg / mL, or It may be about 30 mg / mL to about 40 mg / mL, but is not limited thereto. The dispersion concentration may be about 110 mg / mL or more, but clumping may occur.

In one embodiment of the present application, when dispersing in NMP through sonication, in the case of AZIF-67-Bu ₃ N5 particles or AZIF-8-Bu ₃ N5 particles, water tank sonication of 1 minute or less even at a high concentration of 110 mg / mL It is possible to disperse also in the treatment, preferably high concentration dispersion is possible even in 30 seconds or less, and at a low concentration of 10 mg / mL, it is possible to disperse even in a time of 10 seconds or less. On the other hand, in the case of ZIF-67 and ZIF-8, it was confirmed that the particles did not disperse when treated with water tank sonication for the same time as the AZIF-67 particles and AZIF-8 particles, and despite the low concentration of 10 mg / mL, complete dispersion This was not done and it was confirmed that sedimentation occurred at the same time as the sonication stopped (FIG. 7). 7 shows the concentration and sonication time of each sample.

In one embodiment of the present application, the AZIF-67-Bu ₃ N5 and AZIF-8-Bu ₃ N5 nanoparticles show long-term dispersion stability with respect to the organic solvent, and the period may be 3 or 7 days (FIG. 8), but is not limited thereto. 8 is a photograph of the state in which the experimental sample of FIG. 7 was left for 3 days. More specifically, AZIF-67-Bu ₃ N5 and AZIF-8-Bu ₃ N5 nanoparticles retain their dispersibility after 3 days despite high concentration dispersion of 110 mg / mL after 40 seconds of water sonication. While no sediment was generated, almost all particles were found to precipitate at a low concentration of 10 mg / mL 3 days after 20 minutes of water sonication in the case of ZIF-67 and ZIF-8. Through this, long-term dispersion stability of the developed AZIF-67 and AZIF-8 nanoparticles was confirmed (FIG. 8).

In one embodiment of the present application, the pore size of the AZIF nanoparticles may be less than or equal to about 1 nm. For example, the pore size of the nanoparticles comprising the zeolite imidazolate-based structure is about 0.1 nm to about 1 nm, about 0.1 nm to about 0.9 nm, about 0.1 nm to about 0.8 nm, about 0.1 nm to about 0.7 nm, about 0.1 nm to about 0.6 nm, about 0.1 nm to about 0.5 nm, about 0.2 nm to about 1 nm, about 0.2 nm to about 0.9 nm, about 0.2 nm to about 0.8 nm, about 0.2 nm to about 0.7 nm, It may be about 0.2 nm to about 0.6 nm, or about 0.2 nm to about 0.5 nm, but is not limited thereto.

Based on the XRD analysis, ZIF-7 is known to be 0.29 nm, ZIF-67 is 0.33 nm, and ZIF-8 is known to be 0.34 nm, but according to embodiments herein, various pore sizes can be adjusted by substituting the type of metal and ligand. It is possible.

In one embodiment of the present application, a hybrid membrane (composite film, composite membrane, hybrid film, separation membrane) in which AZIF-67 and / or AZIF-8 nanoparticles are dispersed in a high concentration in a polymer matrix is provided. 10).

In one embodiment of the present application, the content of AZIF nanoparticles dispersed in the polymer matrix in the hybrid membrane may be about 20% by weight or 30% by weight or more based on the total weight of the separation membrane (FIG. 9). For example, the content of AZIF nanoparticles may be 20% by weight, 30% by weight, 40% by weight, or 50% by weight or more based on the total weight of the separator. The upper limit of the content may be, but is not limited to, 60% by weight, 70% by weight, or 80% by weight. On the other hand, in the case of ZIF-67 and ZIF-8, a non-uniform film was produced even when 30% by weight was introduced, and a hybrid film was not produced at 40% by weight or more.

In one embodiment of the present application, the hybrid membrane has flexible properties (FIG. 9). For example, a hybrid membrane comprising 40% by weight of AZIF-67 exhibits the ability to fold without deformation in its original form. On the other hand, in the case of the hybrid membrane containing 40% by weight in the case of ZIF-67, it was easily broken.

In one embodiment of the present application, in the case of AZIF-67 and AZIF-8 introduced in the hybrid membrane, the nanoparticles are not only polyimide-based polymer matrices, but also hybrid membranes in which AZIF nanoparticles are introduced at high concentrations in various engineering polymer materials. Painter is possible (Figure 10). For example, in the polysulfone polymer material, hybrid membrane production is possible when 40% by weight of AZIF nanoparticles are introduced, and this also shows flexible characteristics (FIG. 10).

In one embodiment of the present application, the AZIF nanoparticles introduced into the hybrid membrane are capable of uniform dispersion within the polymer even at high concentrations. For example, even in the case of a hybrid membrane in which 40% by weight of AZIF nanoparticles is introduced, it has a uniform surface without phase separation of the film surface (Figs. 9 and 10), and even in the cross-section of the membrane, AZIF nanoparticles can be used in various polymer types. Disperses uniformly (Fig. 11). On the other hand, in the case of general ZIF-67 nanoparticles, when 30% by weight was introduced, it was found that the particles aggregate together.

In one embodiment of the present application, the AZIF nanoparticles introduced into the hybrid membrane have high interfacial adhesion (or compatibility) with various engineering polymer materials including polyimide polymer materials (FIG. 11). For ^{example, 6FDA-DAM, Ultem ®,} Matrimid 5218 ®, and look for polymeric materials with good interface adhesion between the PSF such as, but not limited to. On the other hand, in the case of ZIF nanoparticles, it was found that clusters are formed by aggregation of particles and voids are formed at the interface with the polymer (FIG. 11).

In one embodiment herein, the thickness of the hybrid film prepared by dispersing AZIF nanoparticles in a high concentration in a polymer matrix may be 50 nm or more, or 100 nm or more. The upper limit of the thickness is not limited thereto, but may be 10 μm, 50 μm, 100 μm, 200 μm, or 500 μm. In the case of the composite film pre-standing film, it may be 10 μm or less, but is not limited thereto.

In one embodiment of the present application, AZIF nanoparticles have high high purity properties. Purity may be 99% or more or 99.5% or more, but is not limited thereto. For example, in the case of an unreacted organic ligand that may be an impurity, it decomposes at a low temperature, while the AZIF nanoparticles are thermally stable up to about 400 ° C (FIG. 12). When comparing the TGA graphs of AZIF nanoparticles and ZIF nanoparticles, there is no weight change from AZIF to high temperatures above 400 ℃, but in general ZIF-67 and ZIF-8, weight changes occur below 300 ℃, especially ZIF-8. In the case of, it was confirmed that AZIF-67 and AZIF-8 developed through a weight change from about 180 ° C., the decomposition temperature of the organic ligand, had relatively high purity (FIG. 12).

The AZIF nanoparticles may exhibit a mass loss of 3% or less at 400 ° C., specifically 0.01% to 3%, 0.01% to 2%, or 0.1% to 2%, in the TGA experimental conditions herein.

The second aspect of the present application is a method of manufacturing AZIF nanoparticles, a precursor solution comprising a metal precursor, an imidazole-based ligand compound and a first polar solvent is heated under stirring, and an organic base solution is added to the precursor solution heated under stirring. Is added to obtain a suspension comprising a micro-sized chunk comprising a zeolite imidazolate-based structure wherein the crystal structure is adjusted, and adding the second polar solvent to the suspension heated under stirring to add the suspension. Provided is a method of preparing AZIF nanoparticles, comprising diluting and filtering the diluted suspension to obtain nanoparticles comprising the zeolite imidazolate-based structure.

To prepare AZIF nanoparticles according to one embodiment of the present application, first, a precursor solution including a metal precursor, an imidazole-based ligand compound and a first polar solvent is heated under stirring.

Unlike the method of synthesizing ZIF particles, the method of manufacturing AZIF nanoparticles according to one embodiment of the present application simultaneously dissolves the metal precursor and the imidazole-based ligand compound, or separately dissolves the metal precursor and the imidazole-based ligand compound. And dissolving followed by mixing.

In one embodiment of the present application, the metal precursor may include an acetate-based metal salt, but is not limited thereto. For example, the metal precursor may include, but is not limited to, cobalt (Co) acetate tetrahydrate metal salt, zinc (Zn) acetate dihydrate metal salt, and the like.

In one embodiment of the present application, the metal precursor is Co, Zn, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd , Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg and Uub. Acetate salt may be included, but is not limited thereto.

In one embodiment of the present application, the imidazole-based ligand compound may include, but is not limited to, one or more selected from imidazole-based compounds represented by Formula 1 or Formula 2:

[Formula 1]

;

;

[Formula 2]

;

;

In each of Formula 1 and Formula 2,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently H, C1 to C10 linear or branched alkyl groups, halogen, hydroxy, cyano, nitro or aldehyde groups ego,

The A ¹ , A ² , A ³ , and A ⁴ are each independently C or N, provided that R ⁵ , R ⁶ , R ⁷ , and R ⁸ are present only when A ¹ and A ⁴ are C .

In one embodiment of the present application, the molar ratio of the metal precursor and the imidazole-based ligand compound may be about 1: 1 to about 1:10, and may be 1: 2, but is not limited thereto. For example, the molar ratio of the metal precursor to the imidazole-based ligand compound is about 1: 1 to about 1:10, about 1: 1 to about 1: 8, about 1: 1 to about 1: 6, and about 1: 1 to about 1: 4, about 1: 1 to about 1: 2, about 1: 2 to about 1:10, about 1: 2 to about 1: 8, about 1: 2 to about 1: 6, about 1: 2 to about 1: 4 or about 1: 1 to about 1: 2, but is not limited thereto.

In one embodiment of the present application, the first polar solvent comprises at least one selected from the group consisting of alcohol, ethylene glycol, water, dimethylformamide, dimethylsulfoxide, acetonitrile and dimethylacetamide. It may be, but is not limited to this. However, as the first polar solvent, a solvent having a high basicity and capable of causing a dehydrogenation reaction to the used ligand cannot be used.

In one embodiment of the present application, the concentration of the metal precursor in the precursor solution may be from about 0.01 M to about 0.4 M, but is not limited thereto. For example, the concentration of the metal precursor in the precursor solution is about 0.01 M to about 0.4 M, about 0.01 M to about 0.3 M, about 0.01 M to about 0.2 M, about 0.01 M to about 0.1 M, about 0.01 M to About 0.05 M, about 0.05 M to about 0.4 M, about 0.08 M to about 0.4 M, about 0.08 M to about 0.3 M, about 0.08 M to about 0.2 M, about 0.1 M to about 0.4 M, about 0.1 M to about 0.3 M, or about 0.1 M to about 0.2 M, but is not limited thereto.

In one embodiment of the present application, the heating temperature of the precursor solution may range from about 30 ° C to about 90 ° C, but is not limited thereto. For example, the heating temperature of the precursor solution is about 30 ° C to about 80 ° C, about 30 ° C to about 70 ° C, about 30 ° C to about 65 ° C, about 30 ° C to about 60 ° C, or about 30 ° C to about 50 ℃ may be, but is not limited thereto.

In one embodiment of the present application, the heating temperature of the precursor solution may be maintained at isothermal, but is not limited thereto. The precursor solution is a solution in a transparent state, and may be in a state in which crystalline ZIF particles are not formed. At this time, one of the metal (M) salt of the metal precursor and the ligand (L) of the imidazole-based ligand compound exist in a combined state, and have a structure as in the following Chemical Formula 4. As shown in the following Chemical Formula 4, the basic structure is L-M-L, and the amine of the ligand is in a state in which dehydrogenation hardly proceeds, and is difficult to bond with one or more metal ions. However, even if the amine of the imidazole-based ligand compound has undergone dehydrogenation to form ZIF nanoparticles, it is a precursor aggregate of small units that cannot be defined as a crystalline substance. If the heating temperature is not isothermal, there is a difference in the components of the obtained ZIF particles, the uniformity of the particle size decreases, and accordingly, precipitates are found or opaque in the precursor solution, which results in reduced metal. Differences have already been made or ZIF particles have been generated, resulting in differences in size and composition of the AZIF nanoparticles obtained in the final step.

[Formula 4]

1 is data according to Embodiment 1 of the present invention. In the synthesis of AZIF-67-Bu ₃ N ₅ particles, the change according to the change in reaction temperature over time is divided into four steps from S1 to S4, and the color of the solution and each solution are diluted with NMP to generate dynamic light scattering. , DLS). According to the DLS analysis results, particles were not detected in S1 and S2.

Referring to FIG. 1, until the organic base solution is added, the initial color of the solution is transparent pink, and after the organic base solution is added, the color changes to purple.

Through the DLS analysis results of the solution obtained in the above 4 steps, in the steps S1 and S2 having a pink solution, the particles are synthesized from the step S3, which is the step of adding the organic base solution, rather than the synthesis of the AZIF-67 particles.

The binding structure of the synthesized particles is as shown in Chemical Formula 5, the basic structure is LML, and the amine of the ligand is in a state in which dehydrogenation proceeds and can be combined with other metal precursors, and additionally, the alkylamine is the second organic ligand. It may have a structure included as (Formula 5).

[Formula 5]

The ZIF-67 particles synthesized in step S3 have two types of particle size groups of ~ 30 nm and ~ 2 μm.

6 and 11 are SEM images taken after simple sonication of the sample corresponding to S4 in FIG. 1 and NMP after purification. 6 and 11, the initially synthesized AZIF-67 particles exist in a micro-sized chunk form, and after purification, dispersion in NMP may result in nano-sized particle size.

In one embodiment of the present application, the stirring time of the organic precursor solution may be about 10 minutes to about 36 hours, but is not limited thereto. For example, the stirring time of the organic precursor solution is about 10 minutes to about 36 hours, about 10 minutes to about 24 hours, about 10 minutes to about 12 hours, about 10 minutes to about 6 hours, about 10 minutes to about 1 Hours, about 10 minutes to about 30 minutes, about 30 minutes to about 36 hours, about 1 hour to about 36 hours, about 12 hours to about 36 hours, or about 24 hours to about 36 hours, but is not limited thereto. no. When the stirring time exceeds about 36 hours, the metal salt may be reduced to produce AZIF nanoparticles containing reduced metal, and if the temperature exceeds the suitable temperature range, the stirring time may be reduced or increased.

Subsequently, an organic base solution is added to the precursor solution heated under the stirring to obtain a suspension containing micro-sized chunks.

The organic base solution can be added between 5 seconds and 5 minutes, and can be added within 30 seconds. When the addition time of the organic base solution exceeds about 5 minutes, the composition and performance of the final product may be affected, and the yield of AZIF nanoparticles may be reduced. In addition, it is preferable to continuously add a certain amount as possible in the addition rate.

In one embodiment of the present application, a micro-sized chunk comprising the zeolite imidazolate-based structure may have a size of about 1 μm to about 10 μm, but is not limited thereto. For example, the size of a micro-sized chunk comprising the zeolite imidazolate-based structure is about 1 μm to about 10 μm, about 1 μm to about 9 μm, about 1 μm to about 8 μm, about 1 μm to about 7 μm, about 1 μm to about 6 μm, about 1 μm to about 5 μm, about 1 μm to about 4 μm, about 1 μm to about 3 μm, about 1 μm to about 2 μm, about 2 μm to about 10 μm , About 3 μm to about 10 μm, about 4 μm to about 10 μm, about 5 μm to about 10 μm, about 6 μm to about 10 μm, about 7 μm to about 10 μm, about 8 μm to about 10 μm, about 9 μm to about 10 μm, about 2 μm to about 9 μm, about 3 μm to about 8 μm, about 4 μm to about 7 μm, or about 5 μm to about 6 μm, but is not limited thereto.

In one embodiment of the present application, the organic base solution may include one or more organic bases selected from the group consisting of primary amines, secondary amines, and tertiary amines.

In one embodiment of the present application, the primary amine, secondary amine, and tertiary amine may each independently be an amine compound represented by Formula 3 below:

[Formula 3]

In Chemical Formula 3,

R ⁹ , R ¹⁰ and R ¹¹ are each independently H, or a C1 to C18 linear or branched alkyl group.

In one embodiment of the present application, pKa of the organic base solution may be greater than about 7. For example, the pKa value of the organic base solution is greater than about 7, about 7.5 or more, 7.8 or more, about 8 or more, about 9 or more, about 10 or more, about 11 or more, about 12 or more, about 13 or more, or about 14 days You can. Also, for example, pKa may be 7 to 10, 7 to 12, or 7 to 14. When the pKa value is less than 7, crystalline AZIF particles are not formed, or the yield of crystalline AZIF particles is greatly reduced.

In addition, a second polar solvent is added to the suspension heated under the stirring to dilute the suspension.

In one embodiment of the present application, the second polar solvent is preferably a solvent having a good solubility in the metal salt and ligand used in the reaction exceeds pH 5. The pH of the second polar solvent may be 5 to 7, 5 to 9 or 5 to 11. For example, it may include one or more selected from the group consisting of alcohol, methanol, ethanol, propanol, ethylene glycol, water, dimethylformamide, dimethylsulfoxide, acetonitrile and dimethylacetamide. However, it is not limited thereto. When the pH of the second polar solvent is 5 or less, the zeolite imidazolate-based structure of the nanoparticles to be synthesized may be damaged. In addition, the second polar solvent preferably has good solubility for unreacted reactants, that is, metal precursor and ligand.

In addition, after diluting the suspension, the additional stirring time may be from about 1 minute to about 10 minutes, and when it exceeds 10 minutes, the size of the chunk, which was a micro size, decreases, making it difficult to apply to tablets through a filter or the yield can be greatly reduced. However, it is not limited thereto. Finally, the diluted suspension is filtered to obtain AZIF nanoparticles.

In one embodiment of the present application, the filter may be a vacuum filter when filtering, and the type of the filter may be paper, metal, glass, plastic, ceramic, etc., but is not limited thereto. However, when water is used as the solvent, the use of paper or Teflon-based filter paper is unsuitable. If a solvent capable of dissolving the plastic is used, plastic cannot be used.

In one embodiment of the present application, the pore size of the filter may be from about 1 μm to about 8 μm. For example, the pore size of the filter is about 1 μm to about 8 μm, about 1 μm to about 7 μm, about 1 μm to about 6 μm, about 1 μm to about 5 μm, about 1 μm to about 4 μm , About 1 μm to about 3 μm, about 1 μm to about 2 μm, but is not limited thereto. When the pore size of the filter is less than about 1 μm, the time required for filtering may be significantly longer, and when it is about 8 μm or more, the filtering may not be performed or the yield may be significantly reduced.

In one embodiment of the present application, the diluted suspension may further include stirring for about 10 minutes or less before the filtering or stopping without stirring, but is not limited thereto.

The manufacturing method according to one embodiment of the present application may further include drying the obtained AZIF nanoparticles.

In one embodiment of the present application, the drying may be performed at a temperature of about 30 ° C to about 110 ° C, and the drying temperature is most preferably about 80 ° C, but is not limited thereto. For example, the drying temperature is about 30 ℃ to about 110 ℃, about 40 ℃ to about 100 ℃, about 50 ℃ to about 90 ℃, about 60 ℃ to about 80 ℃, about 70 ℃ to about 80 ℃, about 80 ℃ to about 90 ℃, or about 70 ℃ to about 90 ℃, but is not limited thereto.

The method of manufacturing AZIF nanoparticles according to one embodiment of the present application exhibits high yield and is capable of mass synthesis. Here, the high yield (yield) means that the weight ratio of the AZIF nanoparticles obtained based on the weight of the metal and ligand precursor contained in the AZIF structure is higher than about 80%. The nanoparticles containing the ZIF structure may be obtained in a ratio of about 30% to about 97% depending on the addition ratio of the organic base solution, but the yield of the obtained AZIF nanoparticles is about 85% to about 95% It is preferred, but is not limited thereto.

Hereinafter, the present application will be described in more detail with reference to examples, but the present application is not limited thereto. The experimental data described above are obtained by experimenting with the samples obtained in the examples below.

[Example 1]

2-methylimidazole (39.55 g) and Cobalt (II) acetate tetrahydrate (60 g) were placed in a 3 L RB flask and 1416.8 mL of methanol was added to dissolve well through stirring for 10 minutes. The heating mantle was used to turn the sterling for 10 minutes while maintaining the isothermal temperature at 60 ° C. After that, tributylamine (Bu ₃ N, 286.2 mL) was rapidly added in a strong sterling state and the sterling was maintained for 1 minute. After that, 1 L methanol was further added, and the stirring was further performed for 1 minute, and the stirring was stopped. Filtering was carried out using cellulose filter paper, and the filtered solid material was purified using additional 1.5 L of methanol. The solid material obtained after the purification was placed in a vacuum oven at 80 ° C. and dried for 24 hours. The weight of the obtained _{ZIF-67-Bu 3 N-} 5 was 51.5 g This was a ZIF-67 component, the Co ^{2 +} and 2-methylimidazole synthesis which corresponds to about 95.7 percent compared to the weight (53.8 g) introducing the synthesis of the The yield was shown.

[Example 2]

ZIF-67 particles containing Bu ₂ N using the same method and the molar ratio (Metal: Ligand: Base = 1: 2: 5) as in Example 1, but using another organic base dibutylamine (Bu ₂ N) (AZIF-67-Bu ₂ N5).

[Example 3]

ZIF-67 particles containing Bu ₁ N using the same method and molar ratio (Metal: Ligand: Base = 1: 2: 5) as in Example 1, but using another organic base, butylamine (Bu ₁ N) (AZIF-67-Bu ₁ N5).

In addition, various AZIF-67 and AZIF-8 nanoparticles were obtained while changing the type and amount of alkyl amine in the same manner as in the above example.

14 is a result of ¹ H NMR analysis obtained after collapsing a crystal structure using an acid after synthesizing AZIF nanoparticles prepared in Example. 14 shows the structure of the 2-methylimidazole component and the organic base together with the analyzed ¹ H NMR spectrum. In addition, the chemical structure corresponding to each peak is marked the same. ^{Through 1} H NMR analysis, it was confirmed that the organic base was included in the AZIF-67 structure, and the amount of the organic base was introduced was controlled through a phenomenon in which the observed peak size of the organic base increased as the amount applied during synthesis increased. It was confirmed that this is possible.

Table 1 below summarizes the molar ratio and the ratio of the ligand to the organic base in the obtained particles in the reactants introduced during synthesis of the AZIF-67 nanoparticles synthesized through the above example. In particular, although the molar ratio of Bu ₃ N introduced from AZIF-67 where Bu ₃ N was introduced was greatly improved and applied from 5 to 10 compared to the cobalt precursor, it was confirmed that the ratio of introduced Bu ₃ N did not show a significant difference. Did.

Co: 2mim: Bu ₁ N 2mim / Bu ₁ N
(wt%) AZIF-67-Bu ₁ N1 1: 2: 1 98.9 / 1.1 AZIF-67-Bu ₁ N2 1: 2: 2 97.9 / 2.1 AZIF-67-Bu ₁ N3 1: 2: 3 97.0 / 3.0 AZIF-67-Bu ₁ N5 1: 2: 5 95.6 / 4.4 Co: 2mim: Bu ₂ N 2mim / Bu ₂ N
(wt%) AZIF-67-Bu ₂ N1 1: 2: 1 98.8 / 1.2 AZIF-67-Bu ₂ N2 1: 2: 2 97.2 / 2.8 AZIF-67-Bu ₂ N3 1: 2: 3 95.2 / 4.8 AZIF-67-Bu ₂ N5 1: 2: 5 93.5 / 6.5 Co: 2mim: Bu ₃ N 2mim / Bu ₃ N
(wt%) AZIF-67-Bu ₃ N1 1: 2: 1 91.6 / 8.4 AZIF-67-Bu ₃ N2 1: 2: 2 85.8 / 14.2 AZIF-67-Bu ₃ N3 1: 2: 3 84.7 / 15.3 AZIF-67-Bu ₃ N5 1: 2: 5 81.6 / 18.4 AZIF-67-Bu ₃ N5 (Scale-up) 1: 2: 5 81.6 / 18.4 AZIF-67-Bu ₃ N10 1: 2: 10 80.3 / 19.7

[Example 4]

ZIF-67 nanoparticles containing Bu ₃ N5 using the same method and the molar ratio (Metal: Ligand: Base = 1: 2: 5) as in Example 1, but using 180 g of Cobalt (II) acetate tetrahydrate applied ( AZIF-67-Bu ₃ N5). The amount of nanoparticles finally obtained was 155 g, showing a yield of 96.2% compared to 161.1 g, which is the weight of 100% of cobalt ion and 2-methylimidazole (FIG. 15).

In addition, it was confirmed that the reproducibility was high through the fact that the weight ratio of 2 mim / Bu ₃ N shown in Table 1 was almost the same as that of the nanoparticles of AZIF-67-Bu ₃ N synthesized at a low scale of 81.6 / 18.4. (Table 1).

[Example 5]

Embodiments, but one and the same way, other organic base of triethylamine (Et ₃ N) for use by Et ₃ N comprises a ZIF-67 nanoparticles, the nano alternating synthesis a molar ratio of Et ₃ N from 1 to 9 Particles (AZIF-67-Et ₃ NX, X = 1, 3, 5, 7, 9) were obtained.

The synthesized AZIF-67-Et ₃ NX nanoparticles were confirmed to contain Et ₃ N through ¹ H NMR results analysis in FIG. 16. In addition, it was confirmed by increasing the Et ₃ N ¹ H NMR peak that the introduction amount of Et ₃ N increased as the proportion of Et ₃ N applied to synthesis increased. In addition, XRD analysis was performed to confirm the crystal structure of AZIF-67-Et ₃ N5, and the results are shown in FIG. 4. When compared with general ZIF-67 nanoparticles, the crystal structure was changed in a similar trend to that of AZIF-67-Bu ₃ N5 synthesized by Example 1.

[Example 6]

AZIF-8 nanoparticles were obtained by using the same method and the molar ratio (Metal: Ligand: Base = 1: 2: 5) as in Example 1, but using another metal precursor, Zinc (II) acetate dihydrate.

It was confirmed that the AZIF-8-Bu ₃ N5 nanoparticles contained Bu3N by analyzing the synthesized AZIF-8-Bu ₃ N5 nanoparticles in XRD and ¹ H NMR results in FIGS. 5 and 17. When compared with the crystal structure of the AZIF-67-Bu ₃ N5 obtained in Example 1 it was confirmed that showing a change in the crystal structure similar to the change in the crystal structure.

[Membrane-Example 1]

Nanoparticles 30 minutes AZIF-67-Bu ₃ N ₅ through sonicator Mix AZIF-67-Bu ₃ N ₅ nanoparticles and NMP in a glass bottle to prepare each other hybrid film having different AZIF-67 nano-particle content Disperse uniformly in the solvent. The AZIF-67-Bu ₃ N ₅ nanoparticles were uniformly dispersed in a solvent for 2 minutes using a cone-shaped ultrasonic grinder. AZIF-67-Bu ₃ N ₅ 6FDA-DAM polymer was mixed with a solvent in which nanoparticles were uniformly dispersed, stirred through a roller for 12 hours, and then a glass bottle containing a uniformly dissolved polymer solution was placed in an ultrasonic grinder for 30 minutes. After removing the fine bubbles in the solution, the polymer solution was spread on a glass plate into a thin layer of 150 μm thickness using a casting blade and dried under vacuum at 120 ° C. for 12 hours. After 12 hours, the vitrified hybrid membrane was dried once again under vacuum at 120 ° C. for 12 hours to remove residual solvent. The hybrid membranes obtained at this time are shown in FIGS. 9 and 10 and showed uniformity and flexibility even when various types of polymers such as Polysulfone (PSF) and Matrimid 5215 ^® were applied and high concentration of AZIF-67 was applied (FIG. 10). As the amount of NMP used in the hybrid membrane manufacturing process, NMP of 9 times the mass of the hybrid membrane was used. In this way, hybrid membranes having various AZIF-67 contents were prepared.

[Membrane-Example 2]

A hybrid membrane was prepared using the same method and weight ratio as the membrane-Example 1, but using other nanoparticles (AZIF-8-Bu ₃ N5) (FIG. 10). At this time, the polymer used was a PI-based polymer called Polyetherimide (Ultem ^® ), and it was confirmed that it exhibits uniformity and flexibility as in the membrane-hybrid membrane obtained in Example 1 (FIG. 10).

[Membrane-Comparative Example 1]

AZIF-67 nanoparticles were replaced with ZIF-67 nanoparticles, and a membrane-hybrid membrane was prepared in the same manner as in Example 1.

[Comparative Example 1: ZIF-67 production]

Under room temperature conditions, 2-methylimidazole (22.70 g) and distilled water (80 g) were mixed in a 100 mL glass vial and dissolved well by stirring at 300 rpm for 5 minutes. In a 100 mL glass vial, Cobalt (II) nitrate hexahydrate (1.17 g) and distilled water (8 g) were mixed and dissolved through stirring at 300 rpm for 5 minutes. Thereafter, the two solutions were mixed in a 400 mL flask and precipitated for 12 hours at room temperature. A total of six plastic containers were prepared by placing the precipitation solution in a plastic container for a 50 mL centrifuge at 18 mL, and centrifugation was performed for 30 minutes at a speed of 8000 rpm. For purification of ZIF-67 particles obtained after centrifugation, filtering was performed using cellulose filter paper, and the filtered solid material was purified three times using 500 mL of methanol. The purified ZIF-67 particles were dried under vacuum conditions at 100 ° C. for 12 hours. The weight of the obtained ZIF-67 particles was about 0.6 g.

[Comparative Example 2: Preparation of ZIF-8]

Under room temperature conditions, 2-methylimidazole (22.70 g) and distilled water (80 g) were mixed in a 100 mL glass vial and dissolved through stirring at 300 rpm for 5 minutes. Zinc (II) nitrate hexahydrate (1.90 g) and distilled water (8 g) were mixed in a 100 mL glass vial and dissolved through stirring at 300 rpm for 5 minutes. Subsequent synthesis was conducted in the same manner as in the ZIF-67 synthesis method, and the weight of the obtained ZIF-8 particles was about 0.8 g.

[Experimental Example 1]

In order to analyze the crystal structure of AZIF-67 nanoparticles, X-ray diffraction (XRD) was used to compare with general ZIF-67 particles. The measurement was measured at 0.01 ° intervals from 5 ° to 30 ° at 2θ based on CuKα λ = 1.5406 A ° at room temperature using a Rigaku Dmax2500 diffractometer.

3 to 5, in the case of AZIF-8 and AZIF-67 nanoparticles, the crystal structure showed a relatively reduced crystal plane spacing compared to general ZIF-8 and ZIF-67 particles, and Bu ₃ N was used as a metal. When the 10 molar ratio compared to the precursor was used, the (002) and (112) crystal planes showed a large growth, and Hx3N showed the same tendency even when the molar ratio was 50,000. Through this, it was confirmed that the sodalite (SOD) structure, which is the basic ZIF-67 and ZIF-8 structure, was maintained except for the change in the spacing of the crystal planes and the formation of a specific crystal plane (FIGS. 3 and 4). In addition, it was confirmed that the AZIF-8 nanoparticles had a similar change to the crystal structure of the AZIF-67 nanoparticles (FIG. 5).

[Experimental Example 2]

Thermogravimetric Analysis (TGA) was performed to evaluate the thermal stability of AZIF-67 and AZIF particles in which various alkylamine groups were introduced. The measurement was performed using a Mettler Toledo TGA1 equipment, and a flow rate of 50 cc / min was flowed under N ₂ gas conditions, and the weight change of each particle according to the temperature change at a heating rate of 5 ° C./min from 25 ° C. to 800 ° C. was recorded.

As shown in FIG. 12, in the case of ZIF-67 particles, the weight of the particles began to decrease from around 250 ° C, and it was confirmed that the particle weight of about 15 wt% decreased around 500 ° C.

[Experimental Example 3]

For the surface area analysis of the AZIF-67 and AZIF-8 nanoparticles introduced with the alkylamine group, ZIF-67 and ZIF-8 nanoparticles were compared using Brunauer-Emmett-Teller (BET) equipment. The measurement was performed under N ₂ 77K conditions using Micromeritics ASAP 2020, and the particles were used after pre-treatment for 3 hours under a vacuum condition of 120 ° C. before BET measurement.

As shown in FIG. 18, when comparing the general ZIF-67 and AZIF-8 in the isothermal analysis graph according to the pressure change of the AZIF-67 and AZIF-8 nanoparticles into which the alkylamine group was introduced, a similar tendency was observed. When using a 10 molar ratio compared to the metal precursor, the N ₂ adsorption curve was decreased.

[Experimental Example 4]

The change in mechanical bond strength between organic ligands and metals (metal ions) in AZIF-67 and AZIF-8 nanoparticles was analyzed by Fourier transform infrared spectroscopy (FT-IR) (FIG. 19). Measurements are taken at Thermo Fisher Scientific Inc. at room temperature. The wave number range from 400 cm ^-1 to 4000 cm ^-1 was scanned at 1.9285 cm / sec using Nicolet iS50 from. Each measurement sample was prepared using potassium bromide (KBr, ≥99% FT-IR grade) purchased from Sigma Aldrich, mixing particles and KBr at a ratio of 1: 100 by weight, and then compressing them into circular pellets with a diameter of 1 cm. .

As shown in FIG. 19, in the case of AZIF nanoparticles, it was confirmed that the pick moves with a relatively high wavenumber compared to ZIF nanoparticles. Through this, it was confirmed that the binding strength of the metal and the organic ligand was relatively higher through the introduction of the alkylamine, and that the change occurred in the AZIF-8.

More specifically, in the case of general ZIF-67, a peak related to the binding (N-Co) of an amine and a metal ion of an organic linker appears at 424.4 cm ^-1 . In the case of AZIF-67-Bu ₃ N ₅ , the peak As it moves to 426.2 cm ^-1 , it shows a difference of approximately 1.8 cm ^-1 . In the case of ZIF-8, 419.1 cm ^-1 shows N-Zn-related picks, and in the case of AZIF-8-Bu ₃ N ₅ , 421.6 cm ^A pick appears at ^-1 , showing a difference of about 2.5cm ^-1 . In addition, in the case of AZIF, the degree of amine binding between the metal ion and the ligand seems to be more constant through a more narrow dispersion. For example, in the case of ZIF nanoparticles, there are various types of defects such as metal vacancy, dangling linker, or linker vacancy, so the number and type of MN bonds in the basic unit cell are various, so that the MN bond strength is various. You can. In the case of AZIF, it seems that the alkylamine promotes the dehydrogenation of the organic binder, thereby promoting crystal growth, and the alkylamine can bind to a linker vacancy to have a more uniform MN binding strength. Through this, it was confirmed that the alkylamine was directly bonded to the metal.

The IR peak of Co-N of AZIF-67 nanoparticles can be increased by 1 to 3 cm ^-1 by an alkylamine-based organic ligand. That is, the IR peak of Co-N is increased by 1 to 3 cm ^-1 compared to ZIF-67 nanoparticles. Likewise, the IR peak of Zn-N of AZIF-8 nanoparticles can be increased by 1.5 to 4 cm ^-1 by alkylamine-based organic ligands.

[Experimental Example 5]

For the AZIF-67 nanoparticles and hybrid membranes, cross-sections of the membranes were taken using a scanning electron microscope (SEM). Inspect F FEG-SEM equipment under normal temperature and vacuum conditions.

As shown in FIG. 6, the size of the AZIF-67 particles was confirmed to be about 50 nm, but when combined with the DLS results of FIG. 1, the size is not limited to 50 nm and may be smaller. As shown in FIG. 11, in the case of the AZIF-67-based hybrid membrane of Example 7, it was confirmed that even when nanoparticles were introduced at a high concentration, the nanoparticles were evenly dispersed in the polymer matrix without agglomeration. In addition, it was confirmed that the compatibility between the polymer and the particle is very good.

The above description of the present application is for illustrative purposes, and those skilled in the art to which the present application pertains will understand that it is possible to easily modify to other specific forms without changing the technical spirit or essential features of the present application.

Claims (22)

In nanoparticles comprising a zeolitic Imidazolate framework (ZIF),
Metal ions;
It contains an organic ligand bound to the metal ion,
The organic ligand is a nanoparticle comprising an imidazolate-based organic ligand and an alkyl amine-based organic ligand. According to claim 1,
Nanoparticles in which at least one of the spacing of the crystal planes, the distribution of the crystal planes, and the bonding strength is controlled according to the use ratio of the alkylamine-based organic ligand. According to claim 2,
The alkyl amine-based organic ligand is a nanoparticle that is directly bonded to the metal ion. According to claim 2,
The alkyl amine-based organic ligand,
At least one of primary, secondary and tertiary amines,
Methyl, ethyl, propyl, butyl, pentyl, hexyl, epsil, octyl, nonyl, decyl, undecyl, dodecyl, propadecyl, butadecyl, pentadecyl, hexadecyl, eptadecyl, octadecyl and nodecyl Nanoparticles comprising at least one selected from the group of alkyl amines having an alkyl chain of length. According to claim 2,
The ratio of the organic ligand to the imidazolate-based organic ligand to the alkyl amine-based organic ligand is 99.9 wt%: 0.1 wt% to 80 wt% to 20 wt%. According to claim 2,
When the metal ion is cobalt, the spacing of the crystal surface of the AZIF nanoparticles is 11.9Å to 12.15Å,
When the metal ion is zinc, the spacing between the crystal surfaces of the AZIF nanoparticles is 12.0 mm 2 to 12.25 mm 2. According to claim 2,
The nanoparticles are nanoparticles having a size of 100 nm or less. The method of claim 7,
The nanoparticles are nanoparticles having a size of 50 nm or less. According to claim 2,
The nanoparticles are nanoparticles that can be dispersed in an amphiphilic solvent. The method of claim 9,
The nanoparticles are nanoparticles that can be dispersed in an amphiphilic solvent to a concentration of about 110 mg / mL. According to claim 2,
The nanoparticles have pores of 0.1 nm to 1 nm. According to claim 2,
The nanoparticles are nanoparticles capable of producing a hybrid membrane by dispersing 20% to 60% by weight in a polymer matrix. According to claim 2,
The nanoparticles are nanoparticles that exhibit a mass loss of about 3% or less within 400 ° C in a TGA experiment. According to claim 2,
When the metal ion is cobalt, the IR peak of Co-N of the AZIF nanoparticles is increased by 1 to 3 cm ^-1 by the alkylamine-based organic ligand,
When the metal ion is zinc, the IR peak of Zn-N of the AZIF nanoparticles is increased by 1.5 to 4 cm ^-1 by the alkylamine-based organic ligand. In the method for producing nanoparticles comprising a zeolite imidazolate-based structure (alkyl amine-zeolitic Imidazolate framework, AZIF),
Heating the precursor solution containing the metal precursor, the imidazole-based ligand compound, and the first polar solvent under stirring;
Adding an organic base solution to the precursor solution to obtain a suspension comprising micro-sized chunks comprising the zeolite imidazolate-based structure;
Diluting the suspension by adding a second polar solvent to the suspension; And
Obtaining nanoparticles comprising the zeolite imidazolate-based structure from the diluted suspension;
A method of manufacturing nanoparticles comprising a zeolite imidazolate-based structure having a controlled crystal structure. The method of claim 15,
The metal precursors are Co, Zn, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg and Uub containing acetate salts of at least one metal selected from the group consisting of Method of manufacturing nanoparticles. The method of claim 15,
The imidazole-based ligand compound comprises one or more selected from the imidazole-based compound represented by the following formula (1) or formula (2), the method of producing nanoparticles.
[Formula 1]

;
[Formula 2]

;
In each of Formula 1 and Formula 2,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently H, C1 to C10 alkyl group, halogen, hydroxy, cyano, nitro or aldehyde group,
A ¹ , A ² , A ³ , and A ⁴ are each independently C or N,
However, R ⁵ , R ⁶ , R ⁷ , and R ⁸ exist only when A ¹ and A ⁴ are C. The method of claim 15,
The first polar solvent and the second polar solvent are each independently alcohol, methanol, ethanol, propanol, ethylene glycol, water, dimethylformamide, dimethyl sulfoxide, acetonitrile, and dimethylacetamide. The method comprising the one or more selected from the group consisting of, nanoparticles. The method of claim 15,
The method of producing nanoparticles having a pH higher than 5 of the second polar solvent. The method of claim 15,
The heating of the precursor solution is a method for producing nanoparticles that is performed isothermally. The method of claim 15,
The organic base solution includes an alkyl amine-based organic ligand,
The alkyl amine-based organic ligand,
At least one of primary, secondary and tertiary amines,
Methyl, ethyl, propyl, butyl, pentyl, hexyl, epsil, octyl, nonyl, decyl, undecyl, dodecyl, propadecyl, butadecyl, pentadecyl, hexadecyl, eptadecyl, octadecyl and nodecyl Method of producing nanoparticles comprising at least one selected from the group of alkyl amines having an alkyl chain of the length. The method of claim 15,
The method of preparing nanoparticles having a pKa of 7 or higher in the organic base solution.

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