KR102601057B1 - Multifunctional Supramolecular Hybrids Encompassing Hierarchical Self-Ordering of Metal-Organic Framework Nanoparticles, and Method of Preparing same - Google Patents

Abstract

A supramolecular metal-organic structure material that is a reaction product of a copper compound, a trialkylamine represented by the following formula (1), and benzene substituted with three or more carboxyl groups, a manufacturing method thereof, a molded article containing the material, and an electronic material containing the molded article It's about devices.
[Formula 1]

In Formula 1,
R ¹ , R ² and R ³ are the same or different from each other and are each independently a C1 to C10 alkyl group.

Description

Multifunctional Supramolecular Hybrids Encompassing Hierarchical Self-Ordering of Metal-Organic Framework Nanoparticles, and Method of Preparing same}

It relates to a multifunctional supramolecular hybrid containing hierarchical self-aligned metal-organic structure nanoparticles, and a method for manufacturing the same.

Metal-organic frameworks (MOFs) are inorganic-organic hybrid materials containing three-dimensional extended structures composed of repeating symmetric units through self-assembled molecular building blocks (Nature 2003, 423, 705-714; Angew. Chem. Int. Ed. 2004, 43, 2334-2375). MOFs, or porous coordination polymers (PCPs), can be designed to prepare crystalline (porous or non-porous) materials of various functionalities by employing multiple coordinating organic linkers and metal ions, which can lead to many chemical and physical properties. It results in characteristics. MOFs contain three-dimensional crystalline nanoporous structures with very large internal surface areas, usually exceeding about 1,000 m ² /g.

The design potential of MOFs allows researchers to fabricate new materials for applications in gas separation/storage, fuel cells, optical sensors, porous magnetic materials, stereoisomer separation/catalysis, photocatalysis, and molecular sieving. (Chem. Soc. Rev. 2008, 37, 191-214; Chem. Soc. Rev. 2009, 38, 1284-1293).

Because MOFs are usually obtained as single crystalline materials, synthesis conditions have a significant impact on the physico-chemical properties of the resulting product. For example, by varying temperature, pressure, solvent, and pH conditions, the study of MOF materials allows for changes in crystal structure, particle size, and coordination mode (which ultimately determine the formative properties of the final product). It shows remarkable changes (Chem. Comm. 2006, 46, 4780-4795).

Despite being single-crystal materials, several new materials based on MOFs have been fabricated in recent years. For example, polymer blends or quantum dot doped MOF composites have been reported to have improved mechanical and optical properties for improved performance as host materials for gas separation/storage or catalytic/magnetic/optical applications (Energy & Environmental Science 2010, 3, 343-351; Nat. Chem. 2012, 4.4, 310-316).

Recently, MOFs in thin films with electrical applications have been developed (US 20140045074 A1; Angew. Chem. Int. Ed. 2011, 50, 6543-6547; Science 2014, 343, 66-69; J. Phys. Chem. C 2014 , 118, 16328-16334). Surprisingly, the MOF material, named HKUST-1 (Hong Kong University of Science and Technology-1) (Science 1999, 283, 1148-50) and also known as Cu-BTC or Basolite™C300 (BASF trade name), is easily accessible. Due to the possible microporous structure and open copper (Cu) metal sites, it offers a variety of potential applications. Additionally, HKUST-1 features a large internal surface area of approximately 2,100 m ² /g. Recent research has shown numerous important applications in other areas of HKUST-1 besides gas storage/separation, such as proton conductivity, electrical conductivity, chemical separation, Li-S cells, electrospun functional fibers, and toxic ion capture. Shows structural characteristics.

The limiting factors for existing methods involving hybrid materials can be summarized as follows:

Conventional synthesis methods typically require hydrothermal or solvothermal reactions involving organic linkers and metal ion solutions that take several days to one week.

1. A critical parameter for determining optical/catalytic/magnetic and other functional properties depends on the particle size of the MOF material. However, the conventional hydrothermal treatment reaction cannot finely control the exact MOF particle size, and thus produces more widely distributed micron-sized particles.

2. Manufacturing thin-film MOFs requires the use of self-assembled monolayers (SAMs), which are expensive, and this method is impossible for large-area production (Chem. Soc. Rev. 2009, 38, 1418 -1429; J. Am. Chem. Soc. 2014, 136, 24642472; Chem. Comm. 2012, 48, 11901-11903).

3. Many MOF materials have low conductivity. Two important factors, MOF grain boundaries and local charges (poor electron delocalization) within the structure, are responsible for the weak charge transfer in MOFs, forming semiconductors or insulators (Science 2014, 343, 66-69).

4. Demonstration of charge transfer from the metal center in HKUST-1 with the help of an external electron-rich guest (e.g., tetracyanoquinodimethane (TCNQ)) can transform MOFs into electrical conductors. Although shown (Science 2014, 343, 66-69), the measured conductivity decreases sharply when the distance between the two electrodes increases beyond the short gap distance of 100 ㎛. This is an important limitation that limits the practical application of MOF thin films in various fields.

One embodiment seeks to provide a new supramolecular metal-organic framework (MOF) material with controllable physical and chemical properties.

Another embodiment seeks to provide a method for manufacturing the supramolecular metal-organic framework (MOF) material.

Another embodiment seeks to provide a molded article containing the supramolecular metal-organic framework (MOF) material.

Another embodiment seeks to provide an electronic device including the molded product.

One embodiment provides a new supramolecular metal-organic framework (MOF) material with tunable physical and chemical properties.

The supramolecular metal-organic structure material may be a reaction product of a copper compound, a trialkylamine represented by the following formula (1), and benzene substituted with three or more carboxyl groups.

[Formula 1]

In Formula 1,

R ¹ , R ² and R ³ may be the same or different from each other and may each independently be a C1 to C10 alkyl group.

The copper compound may be copper nitrate (Cu(NO ₃ ) ₂ ).

The trialkylamine represented by Formula 1 may be triethylamine (NEt ₃ ).

The benzene substituted with three or more carboxyl groups may be 1,3,5-benzenetricarboxylic acid (BTC).

The reaction can be carried out in a non-aqueous organic solvent.

The non-aqueous organic solvent is C1-C10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), N,N-dimethylacetrimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methyl ethyl ketone (MEK), pyridine, or a combination thereof.

The supramolecular metal-organic structure material may be in a sol state.

The supramolecular metal-organic structure material may be in a gel state.

The supramolecular metal-organic structure material may be a viscoelastic material.

The supramolecular metal-organic structure material may be in the form of nanoparticles.

The supramolecular metal-organic structure material may include a lamella structure.

Another embodiment provides a method for manufacturing the supramolecular metal-organic framework (MOF) material.

The production method may include reacting a copper compound, a trialkylamine represented by Formula 1, and benzene substituted with three or more carboxyl groups in a non-aqueous organic solvent.

The copper compound may be copper nitrate (Cu(NO ₃ ) ₂ ).

The trialkylamine represented by Formula 1 may be triethylamine (NEt ₃ ).

The benzene substituted with three or more carboxyl groups may be 1,3,5-benzenetricarboxylic acid (BTC).

The non-aqueous organic solvent is C1-C10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), N,N-dimethylacetrimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methyl ethyl ketone (MEK), pyridine, or a combination thereof.

The non-aqueous organic solvent may be methanol or ethanol.

The non-aqueous organic solvent may be dimethyl sulfoxide (DMSO).

The non-aqueous organic solvent may be N,N-dimethylformamide (DMF).

The non-aqueous organic solvent may be acetonitrile (ACN).

The manufacturing method may be a method of manufacturing a supramolecular metal-organic structure material in a sol state.

The method for producing the supramolecular metal-organic structure material in the sol state involves reacting a solution containing the copper compound with a solution containing a trialkylamine represented by Formula 1 and benzene substituted with three or more carboxyl groups. may include

The manufacturing method may be a method of manufacturing a gel-state supramolecular metal-organic structure material.

The method for producing the gel-state supramolecular metal-organic structure material may include applying heat to the prepared sol-state supramolecular metal-organic structure material or leaving it to stand for a certain period of time.

The manufacturing method may be a method of manufacturing a supramolecular metal-organic structure material, which is a viscoelastic material.

The method of manufacturing the supramolecular metal-organic structure material, which is a viscoelastic material, may include leaving the prepared gel-state metal-organic structure material for a certain period of time.

The manufacturing method may be a method of manufacturing a supramolecular metal-organic structure material in the form of nanoparticles.

The method for producing the nanoparticle-type supramolecular metal-organic structure material may include drying the prepared gel-state metal-organic structure material.

Another embodiment seeks to provide a molded article containing the supramolecular metal-organic framework (MOF) material.

The molded article may be in a film form.

Another embodiment seeks to provide an electronic device including the molded article.

The supramolecular metal-organic framework (MOF) material according to this embodiment can be manufactured by an easy method and has controllable physical, chemical, and mechanical properties. The material is responsive to multi-stimuli and can be easily molded into various three-dimensional shapes. Accordingly, application of the material in various fields is expected.

Figure 1 is a photograph showing supramolecular MOF hybrid gels (MOGs) prepared from Cu and BTC systems using different organic solvents, where G represents gel, ACN represents acetonitrile, and DMF represents N. , N-Dimethyl Formamide (N, N-Dimethyl Formamide), DMSO stands for Dimethyl Sulfoxide, ETH stands for Ethanol, and MEH stands for Methanol.
Figure 2 is a photograph showing the multi-stimuli responsive sol-gel conversion process of MOG prepared in DMSO solvent.
Figure 3 is a schematic diagram showing the phase change of MOG prepared in ACN solvent to a viscoelastic material.
Figure 4 is an SEM image of MOG prepared in ACN solvent (a) and viscoelastic material formed therefrom (b).
Figure 5 is an SEM image of MOG prepared in DMSO solvent.
Figure 6 is an SEM image of MOG prepared in methanol (MEH) solvent.
Figure 7 is an SEM image of MOG prepared in DMF solvent.
Figure 8 is an SEM image of MOG prepared in ethanol (ETH) solvent.
Figure 9 is an SEM image showing the layered structure of MOG(G?MEH) prepared in methanol solvent, obtained by layering one of the two reactants on top of the other.
Figure 10a is a graph showing the storage modulus (G') obtained 1 hour after manufacturing the supramolecular MOF hybrid gel (MOG).
Figure 10b is a graph showing the loss modulus (G") obtained 1 hour after preparing the supramolecular MOF hybrid gel (MOG).
Figure 10c is a graph showing the shear modulus (G) obtained 1 hour after preparing the supramolecular MOF hybrid gel (MOG).
Figure 10d is a graph showing the loss tangent (tanδ) value according to frequency obtained 1 hour after manufacturing the supramolecular MOF hybrid gel (MOG).
Figures 10e and 10f are graphs showing the results of dynamic deformation sweep measurements performed on a G⊃DMSO sample.
Figure 11a is a graph showing the storage modulus (G') obtained 1 hour, 24 hours, 48 hours, and 72 hours after manufacturing G⊃ACN.
Figure 11b is a graph showing the loss modulus (G") obtained 1 hour, 24 hours, 48 hours, and 72 hours after manufacturing G⊃ACN.
Figure 11c is a graph showing loss tangent (tanδ) values according to frequency obtained about 1 hour, about 24 hours, about 48 hours, and about 72 hours after manufacturing G⊃ACN.
Figure 11d is a graph showing the shear modulus (G) obtained 1 hour, 24 hours, 48 hours, and 72 hours after manufacturing G⊃ACN.
Figure 11e is a graph showing the results of dynamic deformation sweep measurements performed on a viscoelastic material of G⊃ACN.
Figure 11f is a graph showing the results of constant stress creep test after about 24 hours and about 72 hours after manufacturing G⊃ACN.
Figure 12 is a graph of voltage versus current (IV) of supramolecular MOF hybrid gels (MOG), and Figure 12 (b) is a graph showing an enlarged portion of a portion of Figure 12 (a).
Figure 13 is a Nyquist plot of G-ETH with an expanded area in a higher frequency range (inset), and Figure 13 (b) is a graph showing an enlarged portion of a portion of Figure 13 (a). .
Figure 14 is a Nyquist plot of a viscoelastic hybrid material derived from G?ACN, and Figure 14(b) is a graph showing an enlarged portion of a portion of Figure 14(a).
Figure 15 is a photograph showing that when supramolecular metal-organic structure hydride gel (MOG) was dried at room temperature for a long time, the gel became spherical nano-sized metal-organic structure hybrid particles impregnated within the hybrid fiber.
FIG. 16 is a photograph showing that the gel shown in FIG. 15 was immersed in a polar organic solvent for less than 1 minute, thereby destroying all of the gel fibers and generating pure metal-organic structure nanocrystals.
Figure 17 is a photograph showing a MOF thin film deposited on a glass substrate obtained by a sol-gel method, the thickness of which increases from left to right.
Figure 18 is a photograph showing a MOF thin film deposited from a supramolecular metal-organic structure nanoparticle suspension on a glass substrate using dip coating.
Figure 19 is a photograph showing the reversible color change that occurs when the thin film manufactured in Figure 18 is heated to 100°C and cooled back to room temperature.
Figure 20 is a photograph showing the surface shape of the thin film manufactured in Figure 18.
Figure 21 is a profile of the surface roughness of the area indicated by the horizontal line in Figure 20 analyzed by AFM topography.
Figure 22 is a 2D X-ray diffraction graph confirming the crystal structure of the thin film prepared in Figure 18, and the graph below is a 2D The graph shown is a graph simulating the 2D X-ray diffraction of a thin film on which supramolecular metal-organic structure nanoparticles are deposited.
Figure 23 is a photograph showing the setting for measuring the electrical conductivity of supramolecular MOF hybrid gel (MOG) samples.

Hereinafter, with reference to the attached drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

In the drawing, the thickness is enlarged to clearly express various layers and areas.

When a part of a layer, membrane, region, plate, etc. is said to be “on” another part, this includes not only cases where it is “directly above” the other part, but also cases where there is another part in between. Conversely, when a part is said to be “right on top” of another part, it means that there is no other part in between.

Hereinafter, unless otherwise defined, “substitution” means that hydrogen in the compound is a C1 to C30 alkyl group, a C2 to C30 alkynyl group, a C6 to C30 aryl group, a C7 to C30 alkylaryl group, or a C1 to C30 alkyl group. alkoxy group, C1 to C30 heteroalkyl group, C3 to C30 heteroalkylaryl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to C30 cycloalkynyl group, C2 to C30 heterocycloalkyl group. , halogen (-F, -Cl, -Br or -I), hydroxy group (-OH), nitro group (-NO ₂ ), cyano group (-CN), amino group (-NRR' where R and R' are independent of each other is hydrogen or C1 to C6 alkyl group), azido group (-N ₃ ), amidino group (-C(=NH)NH ₂ ), hydrazino group (-NHNH ₂ ), hydrazono group (=N(NH ₂ ), aldehyde group (-C(=O)H), carbamoyl group (-C(O)NH ₂ ), thiol group (-SH), ester group (-C(=O)OR, where R is C1 to C6 alkyl group or C6 to C12 aryl group), carboxyl group (-COOH) or its salt (-C(=O)OM, where M is an organic or inorganic cation), sulfonic acid group (-SO ₃ H) or its salt a salt of (-SO ₃ M, where M is an organic or inorganic cation), a phosphate group (-PO ₃ H ₂ ) or a salt thereof (-PO ₃ MH or -PO ₃ M ₂ , where M is an organic or inorganic cation) ) and combinations thereof.

Additionally, unless otherwise defined below, “hetero” means containing 1 to 3 hetero atoms selected from N, O, S, Si, and P.

As used herein, an “alkylene group” is a straight-chain or branched-chain saturated aliphatic hydrocarbon group having a valence of two or more and optionally containing one or more substituents. As used herein, “arylene group” refers to a functional group that optionally includes one or more substituents and has a valence of two or more formed by removing at least two hydrogens from one or more aromatic rings.

In addition, “aliphatic organic group” refers to a straight or branched chain alkyl group of C1 to C30, “aromatic organic group” refers to an aryl group of C6 to C30 or heteroaryl group of C2 to C30, and “cycloaliphatic organic group” refers to an alkyl group of C1 to C30. It refers to a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, and a C3 to C30 cycloalkynyl group. In addition, a “carbon-carbon unsaturated bond-containing substituent” refers to a C2 to C20 alkenyl group containing at least one carbon-carbon double bond, a C2 to C20 alkynyl group containing at least one carbon-carbon triple bond, or a C2 to C20 alkynyl group containing at least one carbon-carbon triple bond. It may be a C4 to C20 cycloalkenyl group containing at least one carbon-carbon double bond or a C4 to C20 cycloalkynyl group containing at least one carbon-carbon triple bond in the ring.

As used herein, “a combination thereof” means a mixture of constituents, a laminate, a composite, an alloy, a blend, a reaction product, etc.

In one embodiment, a new supramolecular metal-organic framework (hereinafter referred to as “MOF”) hybrid material having controllable physical or chemical properties is provided.

Hereinafter, the new supramolecular metal-organic framework (MOF) hybrid material, its manufacturing method, and the responsivity, phase change, or fine structure change and properties of the material to various stimuli are described in detail with reference to the attached drawings. Explain.

1. New supramolecule Metal-organic framework (MOF) hybrid matter

The copper-based MOF material, HKUST-1 (Science 1999, 283(5405) 1148-50), was synthesized using different solvents, temperatures, or bases (Chem. Mater. 2010, 22, 5216-5221; Chem. Phys. Chem. 2013, 14, 2825-2832; Adv. Funct. Mater. 2011, 21, 1442-1447) has been studied on its supramolecular structural form (Nat. Chem. 2011, 3, 382-387) , Cryst. Eng. Comm. 2011, 13, 3314-3316).

By reacting a high concentration of starting reactants in a small amount of solvent, the present inventors have developed a new supramolecular metal-organic framework (MOF) hybrid material that exhibits completely different physical and chemical properties from previously reported supramolecular metal-organic framework (MOF) hybrid materials. The material was prepared.

Specifically, a new supramolecular metal-organic framework (MOF) hybrid gel was prepared by reacting a copper compound, a trialkylamine represented by the following formula (1), and benzene substituted with three or more carboxyl groups.

[Formula 1]

In Formula 1,

R ¹ , R ² and R ³ are the same or different from each other and may each independently be a C1 to C10 alkyl group, specifically a C1 to C5 alkyl group, and more specifically a C1 to C3 alkyl group. .

More specifically _, a new supramolecular metal- _{organic structure} ( MOF) hybrid gel was prepared.

Reactions performed in various organic solvents were performed on different supramolecular metal-organic gels (MOGs), specifically G⊃ACN, G⊃DMF, G⊃DMSO, G⊃ETH and G⊃MEH. (Here, G represents gel, ACN is acetonitrile, DMF is N, N-Dimethyl Formamide, DMSO is Dimethyl Sulfoxide, ETH is Ethanol, MEH represents methanol) (see Figure 1).

The present inventors have discovered that by using different solvents in preparing metal-organic gels (MOGs), the prepared metal-organic gels (MOGs) exhibit characteristic physical, mechanical, and chemical properties that are tunable. , which also explains the structural dependence of the multifunctionality of the metal-organic gel.

2. Sol-Gel Transitions

The preparation of the supramolecular metal-organic structure, HKUST-1, is well known in the literature, typically by reacting 1,3,5-benzenetricarboxylic acid (BTC) and copper (Cu) together in DMSO solvent. Includes ordering.

However, in this embodiment, by using triethylamine (NEt ₃ ) base, it is completely unexpected and surprising that the self-assembly resulting from the above reaction can produce a completely new hybrid metal-organic gel (MOG) material. It's an effect. As described in detail below with reference to Figure 2, studies have shown that this gel compound exhibits remarkable responses to thermal, mechanical, and chemical stimuli.

The unique multiple reactivity phenomenon can be explained as follows.

In forming MOG, when 1 equivalent of BTC and/or 1.5 equivalents of Cu(II) solution are added alternately in succession, self-assembly or phase transformation occurs, i.e., in a gel. Conversion to sol or from sol to gel occurs.

In addition to the cationic Cu(II) and anionic BTC ^{3 -} effects on self-assembly, when stirred and subjected to mechanical force, the material's integrity to turn into a gel is inhibited and it becomes a viscous sol. Surprisingly, the sol can be restored to a gel state by sonicating the sol for about 1 to 2 minutes, or by leaving the sol for 10 to 15 minutes. It was found that this hybrid material is sensitive to agitation, and thus phase recovery (sol to gel) takes longer to occur when stronger mechanical forces are applied.

In addition to chemical and physical reactions, the gel phase of G⊃DMSO can also be created by heating the sol at 80°C for several minutes, specifically for about 1 to about 2 minutes.

3. Metal-organic of gel viscoelasticity hybrid Transformation of Metal-Organic Gels into Viscoelastic Hybrid Materials)

Another unique phase change was found in the G⊃ACN gel prepared using the acetonitrile solvent. That is, the above It was observed that the gel was converted into a solid-like material.

Figure 3 is a schematic diagram schematically showing the phase change of the gel into a viscoelastic material.

As shown in Figure 3, when G⊃ACN was left in a sealed vial for more than 48 hours, the gel changed into a visco-elastic material. One of the important physical properties of this material is its ability to maintain its shape. This material is soft and stable enough to be cut into arbitrary shapes (or deformed by applying slight pressure by hand) and, therefore, can be easily molded into a variety of three-dimensional shapes, complex shapes, and structures. It can be molded.

4. Having a well-ordered microstructure supramolecule hybrid ( Supramolecular Hybrids with Highly Aligned Microstructures)

Figure 4 is a scanning electron micrograph (SEM) photograph of a metal-organic gel (MOG) material (a) prepared using acetonitrile as a solvent, and a viscoelastic material (b) formed therefrom.

Meanwhile, Figures 5 to 8 show metal-organic gel (MOG) materials (indicated by (a) in each figure) prepared using different solvents, namely, DMSO, methanol, DMF, and ethanol; These are scanning electron microscopy (SEM) photographs of gel samples (marked as (b) in each figure) dried from them.

As shown in Figures 5-8, scanning electron microscopy (SEM) images of the dried material described above show that the fibers of the material grow in a certain direction. That is, all dried gel samples show a thick mass with fibers growing in the form of strips of various sizes with different thicknesses.

Figure 9 is an SEM image showing the fibrous network formed as lamella in G·MEH, a metal-organic gel (MOG) prepared using methanol as a solvent.

5. adjustable with mechanical properties supramolecule hybrid ( Supramolecular Hybrids with Tunable Mechanical Properties)

Dynamic rheological experiments are performed to study the structural integrity of the supramolecular hybrid MOF when applying shear deformation (γ) and corresponding shear stress (τ).

Storage modulus (G') and loss modulus (G") are measures of recoverable elastic response and dissipative viscous behavior, respectively.

The shear modulus (G = τ/γ) is It is a value of and reflects the mechanical strength of the material, that is, the structural resistance (stiffness) to distortion caused by shear deformation.

Storage modulus (G') under shear stresses of all gel samples prepared as in Figures 4 to 8 through frequency sweep dynamic rheological study (Dynamic Mechanical Analysis, DMA) and loss modulus (G") were measured and showed different values, which suggests that the mechanical properties of the hybrid material can be adjusted by applying different solvents.

Figures 10a and 10b are graphs showing the storage modulus (G') and loss modulus (G") obtained 1 hour after manufacturing the supramolecular MOF hybrid gel (MOG), respectively, and Figure 10c is a graph showing the storage modulus (G') and loss modulus (G") obtained 1 hour after manufacturing the supramolecular MOF hybrid gel (MOG). This is a graph showing the shear modulus (G) obtained after 1 hour.

Meanwhile, Figure 10d is a graph showing the loss tangent (tanδ = G"/G') value according to frequency obtained 1 hour after manufacturing the supramolecular MOF hybrid gel (MOG).

10A and 10B, G⊃ACN, G⊃DMF, and G⊃ETH have a relatively large storage modulus (G') of about 10 kPa to about 30 kPa and a relatively large loss of about 5 kPa to about 20 kPa. While G⊃DMSO and G⊃MEH have significantly smaller storage moduli (G') of about 1 kPa to about 5 kPa and significantly smaller loss moduli (G") of about 0.5 kPa to about 1.5 kPa. has As a result, as can be seen from Figure 10c, G⊃DMSO and G⊃MEH can achieve extremely small shear modulus.

However, elastic modulus values varied greatly between samples depending on the amount of solvent trapped within the molecules.

As shown in Figure 10d, it can be seen that G⊃ACN, G⊃MEH, and G⊃ETH have characteristic peaks indicating phase changes at a relatively large angular frequency of about 50 Hz to about 100 Hz. In particular, the large deviation observed in G⊃ACN indicates that the hybrid network of G⊃ACN is relatively weaker against shear forces applied at relatively high frequencies. In contrast, G⊃DMSO shows virtually negligible phase change, showing good mechanical stability against shear deformation.

Dynamic strain sweep measurements are performed to investigate the thixotropic nature of the G⊃DMSO samples. Figures 10e and 10f are graphs showing the results of dynamic strain sweep measurements performed on a G⊃DMSO sample.

As shown in Figure 10e, reproducible recovery to the gel state is confirmed within 15 minutes during relaxation of strain from 100% to 0.1% at an angular frequency of 0.1 Hz.

In dynamic strain sweep measurements, the intersection between the storage modulus (G') and the loss modulus (G") is determined as the strain resistance.

As shown in Figure 10f, it can be seen that the G⊃DMSO sample has an internal strain rate of 16%.

Meanwhile, to study the changes in storage modulus (G') and loss modulus (G") as a function of time, the same experiment was performed 1 h, 24 h, and 48 h after fabrication of supramolecular MOF hybrid gel (MOG), respectively. , and repeated 72 hours later.

By monitoring the structural transition of G⊃ACN through rheology, we can see how the transition to a viscoelastic state changes the strength of the entire network.

Figures 11a and 11b are graphs showing the storage modulus (G') and loss modulus (G") obtained 1 hour, 24 hours, 48 hours, and 72 hours after manufacturing G⊃ACN, respectively, and Figure 11c is This is a graph showing loss tangent (tanδ) values according to frequency obtained about 1 hour, about 24 hours, about 48 hours, and about 72 hours after manufacturing G⊃ACN.

Meanwhile, Figure 11d is a graph showing the shear modulus (G) obtained 1 hour, 24 hours, 48 hours, and 72 hours after manufacturing G⊃ACN.

As shown in Figures 11A and 11B, dynamic structural deformation is evidenced by a substantial non-linear increase in the storage modulus (G') over time. For example, at a frequency of 0.1 Hz, G⊃ACN has a storage modulus (G') of about 17 kPa after about 1 hour after manufacturing, about 26 kPa after about 48 hours, and about 45 kPa after about 72 hours. Similarly, at higher frequencies, for example at 100 Hz, G⊃ACN reaches values such that the storage modulus (G') after about 72 hours of manufacture exceeds three times the storage modulus (G') after about 1 hour of manufacture. have

As shown in Figure 11c, when G⊃ACN is left for about 48 hours or more after manufacturing, the loss tangent (tanδ) value is independent of frequency and no phase change is detected. This finding shows that, as shown in Figure 11d, the weak supramolecular network in G⊃ACN becomes increasingly stronger over time and becomes mechanically more resistant to shear-induced deformation, thereby showing in Figure 4(b) As shown, it shows that G⊃ACN is converted into a viscoelastic material with a well-organized microstructure.

Figure 11e is a graph showing the results of dynamic deformation sweep measurements performed on a viscoelastic material of G⊃ACN.

As shown in Figure 11e, it can be seen that the viscoelastic material of G⊃ACN has a strain resistance of 11%.

In addition, constant-stress creep experiments are performed to compare the strain recovery after approximately 24 hours and after approximately 72 hours after G⊃ACN fabrication. Figure 11f is a graph showing the results of constant stress creep test after about 24 hours and about 72 hours after manufacturing G⊃ACN.

As shown in Figure 11f, the sample after about 72 hours of G⊃ACN production, which corresponds to the viscoelastic material of G⊃ACN, showed significantly higher creep resistance and strain recovery response than the sample after about 24 hours of production of G⊃ACN. indicates.

6. adjustable electrically conductive supramolecule hybrid ( Supramolecular Hybrids with Tunable Electrical Conductivity)

Measurements of electrical conductivity show interesting results from the fact that all samples exhibit different conductivity values, thus suggesting the possibility of tuning the electrical properties.

Specifically, when measured using a 10V bias using a Keithley 2614B sourcemeter and a conduction cell containing each metal-organic gel sample prepared above, G⊃MEH was the highest electrical conductivity. It shows a value of 9.4402 S/m, while the lowest conductivity value is observed for GDMSO (0.1388 S/m) (see Figures 12 (a) and 12 (b)).

Figure 12 is a graph of voltage versus current (I-V) of supramolecular MOF hybrid gel (MOG), and Figure 12 (b) is a graph showing an enlarged portion of a portion of Figure 12 (a).

The relatively low conductivity values in G⊃DMF (0.2255 S/m) and G⊃DMSO are due to the fact that their mobility is hindered by solvent molecules that surround and interact strongly with the stable gel phase, thereby suppressing the overall charge mobility. It is thought to be due to the “cage effect” of charge carriers.

The second highest conductivity was observed in G⊃ACN (2.5125 S/m), followed by G⊃ETH (1.1367 S/m).

For G⊃ACN (2.5125 S/m), a relatively low conductivity was initially observed, but surprisingly, the viscoelastic material derived from the same gel sample showed a significantly higher conductivity of 9.8583 S/m, representing an improvement of approximately 300%. . As described in point 3 above, the viscoelastic material can be cut into different shapes and pressed into thin sheets or films, and therefore its relatively high electrical conductivity value increases the potential electron potential of the material. Indicates applicability to the device's intended use.

Meanwhile, in Figure 12(a), the flat part between ±5V appears to be related to the knee voltage of the aluminum electrode of the Keithley 2614B source meter.

Additionally, measurements of alternating current impedance reveal the unique electrical properties of the metal-organic gels as a function of frequency.

A typical Warburg impedance with a small hump is observed in all gel samples prepared above. This suggests strong charge transfer occurring associated with weakly interacting ionic substances and potentially MOF nanoparticles in the samples.

As a result of measuring the ionic conductivity values of the above samples using Nyquist plots, the results were as follows.

Sample ionic conductivity G⊃MEH 4.61 x 10 ^-2 S/cm G⊃ETH 1.5 x 10 ^-2 S/cm G⊃ACN 1.15 x 10 ^-2 S/cm G⊃DMF 8.65 x 10 ^-3 S/cm G⊃DMSO 6.92 x 10 ^-3 S/cm Viscoelastic hybrid materials from G⊃ACN 4 x 10 ^-4 S/cm

In addition, Figure 13 is a Nyquist plot of G⊃ETH with an expanded area in a higher frequency range (inset), and Figure 13 (b) shows an enlarged portion of a section of Figure 13 (a). It's a graph.

Figure 14 is a Nyquist plot of a viscoelastic hybrid material derived from G⊃ACN, and Figure 14(b) is a graph showing an enlarged portion of a portion of Figure 14(a).

7. hybrid Controlled Nanoparticles Fast synthesis for growth (Rapid Synthesis Towards Controlled Growth of Hybrid Nanoparticles )

The method of this embodiment for the production of supramolecular MOF hybrid materials simultaneously allows for controlled production of supramolecular metal-organic structure hybrid nanoparticles from gel fibrous assemblies.

According to the method of this embodiment, nanoparticles having a particle size of about 30 nm to about 150 nm can be produced.

The results of analyzing the particle size of the prepared MOFs using AFM and optical images are shown in Figure 20.

The synthesis method according to this embodiment proposes a rapid synthesis method of nano-sized supramolecular metal-organic structure hybrid materials, and thus proposes a new method that can be developed for industrial mass production.

Figure 15 shows spherical nano-sized metal-organic structure hybrid particles impregnated within hybrid fibers when the metal-organic structure hydride gel (MOG) prepared in the above example was dried at room temperature for a long time. This is a photo showing that it is.

FIG. 16 is a photograph showing that when the gel shown in FIG. 15 is immersed in a polar organic solvent, for example, methanol, for less than 1 minute, all the fibers of the gel are destroyed to produce pure metal-organic structure nanocrystals. .

That is, after generating the metal-organic structure hybrid gel according to this embodiment, drying it, or washing it after drying, can quickly and easily produce metal-organic structure hybrid nanoparticles.

8. supramolecule Metal-Organic in gel Facile Thin Film Fabrication Enabled by Supramolecular Metal-Organic Gels)

Apart from the unique physical properties of the supramolecular MOF hybrid materials described above, one of the advantages of these sol-gel phases is that supramolecular MOF hybrid thin films can be easily prepared. Uniformity in the nano-sized crystal size of the nanoparticles makes it possible to produce a uniform, compact, and flat thin film.

The thin film can be easily prepared on any support using known coating methods, such as dip coating, spin coating, and doctor-blade film coating methods. The support may be a glass substrate, silicon, ITO (Indium Tin Oxide), FTO substrate, etc., but is not limited thereto.

For example, by adding a solvent, such as methanol, to the prepared G⊃MEH gel, the fibrous network of the gel is destroyed to obtain pure nanoparticles, and the solution containing the prepared nanoparticles is spread on a glass substrate, etc. A thin film of the nanoparticles can be obtained by dip coating the surface.

Meanwhile, the thin film can be manufactured with different thicknesses (about 100 nm to about 10 ㎛ thickness) depending on the concentration of the nanoparticle suspension.

In one embodiment, thin films with a thickness of 1㎛, 2㎛, 5㎛, and 10㎛ were manufactured by coating the nanoparticle suspension on a glass substrate using a doctor blade method by adjusting the concentration, and each film produced A photograph is shown in Figure 17.

On the other hand, the sol phase of G⊃DMSO allows the easy preparation of very compact and uniform thin coatings of these hybrid materials. The air-dried coating is immediately cleaned by careful immersion in methanol for about 10 to about 15 minutes, allowing removal of unwanted water-soluble precursors to obtain a pure metal-organic framework nanoparticle film. A photograph of the thin film produced accordingly is shown in Figure 18. The portion indicated by A in Figure 18 shows a thin film formed on an organic substrate.

The thin film marked A in Figure 18 turns green when heated to high temperature if not cleaned, whereas the cleaned film shows the typical color change expected for HKUST-1 thin films, i.e., the coordinated water from the central copper is removed. Accordingly, a color change occurs from cyan to dark blue (see Figure 19).

The thin film produced by the above method exhibits high uniformity, for example, the average particle diameter is about 100 nm or less, specifically about 30 nm or less, and the surface roughness is in the range of about 10 nm to 30 nm.

Specifically, Figure 20 shows the surface shape of the thin film.

From Figure 20, it can be seen that the size of the nanoparticles present in the thin film is approximately 30 nm or less.

Figure 21 is a graph measuring the surface roughness of the horizontal line portion in the photograph of Figure 20 using AFM topography.

From Figure 21, it can be seen that the surface roughness of the produced film is between about 10 nm and 30 nm, indicating that the thin film was formed very uniformly.

Figure 22 is a 2D X-ray diffraction graph confirming the crystal structure of the nanoparticles in the thin film. The graph below is a 2D This is a graph simulating the 2D X-ray diffraction of the deposited thin film.

Example

Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the following examples and comparative examples are for illustrative purposes and are not intended to limit the present invention.

Unless otherwise stated in the present application specification, samples such as metal-organic gels and metal-organic structure hybrid nanoparticles used to describe the supramolecular metal-organic structure material in the present application specification were used in the methods described in the examples below. These were manufactured according to the following, and each test or analysis was performed according to the method described in the test examples below. However, the present invention is not limited thereto.

Example 1: Preparation of metal-organic gel (G?MEH) and metal-organic structure hybrid nanoparticles

1,3,5-Benzenetricarboxylic acid (BTC) is dissolved in methanol to a concentration of about 2mM, and triethylamine is added to a concentration of about 6mM to form a completely soluble ligand solution. do. The fully soluble ligand solution is sonicated for approximately 5 minutes.

Copper nitrate salt is added to methanol to a concentration of about 3 mM, and further sonicated for about 1 to 2 minutes to dissolve it, thereby preparing a copper nitrate solution.

The mixture is then prepared by adding the copper nitrate solution to the completely soluble ligand solution while shaking vigorously for several seconds. Thereafter, the mixture is left until it exhibits gel-like behavior. When left for about 2 minutes, the mixture exhibits a gel-like behavior. Here, the gel-like behavior can be confirmed by the tube inversion method. In this way, a metal-organic gel (G⊃MEH) is prepared.

The metal-organic gel (G⊃MEH) is dried at room temperature. Next, the dried metal-organic gel (G⊃MEH) is immersed in methanol for less than 1 minute and then washed. As a result, metal-organic structure hybrid nanoparticles are formed.

Example 2: Preparation of metal-organic gel (G⊃ETH) and metal-organic structure hybrid nanoparticles

The same method as Example 1 was carried out, except that ethanol was used instead of methanol when preparing the solution in which the fully soluble ligand was formed and when preparing the copper nitrate solution.

In Example 2, the mixture exhibited gel-like behavior when left for about 5 minutes.

Example 3: Preparation of metal-organic gel (G⊃ACN) and metal-organic structure hybrid nanoparticles

The same method as Example 1 was performed except that acetonitrile was used instead of methanol when preparing the solution in which the fully soluble ligand was formed and when preparing the copper nitrate solution.

In Example 3, the mixture exhibits gel-like behavior when left for about 5 minutes.

Example 4: Preparation of metal-organic gel (G⊃DMF) and metal-organic structure hybrid nanoparticles

The same method as Example 1 was performed except that N,N-dimethylformamide was used instead of methanol when preparing the solution in which the fully soluble ligand was formed and the copper nitrate solution.

In Example 4, the mixture exhibits gel-like behavior when left for about 10 minutes.

Example 5: Preparation of metal-organic gel (G⊃DMSO) and metal-organic structure hybrid nanoparticles

The same method as Example 1 was carried out, except that dimethyl sulfoxide was used instead of methanol when preparing the solution in which the fully soluble ligand was formed and when preparing the copper nitrate solution.

In Example 5, the mixture exhibits gel-like behavior when left for about 20 minutes.

Example 6: Thin film manufacturing

The metal-organic gel prepared in Example 1 was used as a precursor for producing a MOF thin film. The metal-organic gel was washed three times using about 20 ml of methanol, and then centrifuged to collect nano-metal-organic framework (NMOF) particles.

The remaining suspension at the bottom of the centrifuge tube is collected, and the suspension is then adjusted to a gap size between the tip of the blade and the surface of the glass substrate ranging from several micrometers to tens of micrometers, specifically about 4 μm. A MOF thin film is formed by depositing on a glass substrate using doctor blade technology while changing the thickness from about 50 ㎛. Additionally, the NMOF suspension can also be successfully used in dip coating and spin coating methods (sequentially i) about 500 rpm for about 50 seconds, ii) about 800 rpm for about 50 seconds, and iii) about 1000 rpm for about 20 seconds.

Example 7: Thin film manufacturing

A thin film was prepared in the same manner as Example 6, except that the metal-organic gel prepared in Example 2 was used instead of the metal-organic gel prepared in Example 1.

Example 8: Thin film manufacturing

A thin film was prepared in the same manner as Example 6, except that the metal-organic gel prepared in Example 3 was used instead of the metal-organic gel prepared in Example 1.

Example 9: Thin film manufacturing

A thin film was prepared in the same manner as Example 6, except that the metal-organic gel prepared in Example 4 was used instead of the metal-organic gel prepared in Example 1.

Example 10: Thin film manufacturing

A thin film was prepared in the same manner as Example 6, except that the metal-organic gel prepared in Example 5 was used instead of the metal-organic gel prepared in Example 1.

Comparative example 1 to 5

In Examples 1 to 5, the reaction was performed using NaOH instead of triethylamine, respectively. When each reaction mixture was left to stand, it was confirmed that a precipitation product was formed instead of a metal-organic gel. Each experiment performed is sequentially referred to as Comparative Examples 1 to 5.

Comparative example 6 to 10

In Examples 1 to 5, the reaction was performed using KOH instead of triethylamine, respectively. When each reaction mixture was left to stand, it was confirmed that a precipitate was formed instead of a metal-organic gel. Each experiment performed is sequentially referred to as Comparative Examples 6 to 10.

Test example 1: Fluidity test

Flow measurements such as storage modulus and loss modulus are performed using a Physica MCR-301 (Anton Paar) rheometer equipped with a temperature-controlled basal plate. All tests use a parallel plate arrangement with a gap of approximately 1 mm between the base plate and the top plates. A constant shear stress of approximately 10 Pa is applied for the creep recovery test and stress recovery test.

Test example 2: scanning electron microscope: S.E.M. ) image

Metal-organic gel specimens are coated with a thin film of gold using a SC7620 Polaron sputter coater (Quorum Technologies). Photographs are then taken using a scanning electron microscope (Carl Zeiss EVO LS15).

Test example 3: infinite focus microscopy: IFM ) analyze

Optical images and surface height topography of the MOF thin film are analyzed using infinite focus microscopy (IFM (Alicona Infinite Focus 3D profilometer)).

Test example 4: X-ray diffraction analysis

X-ray powder diffraction properties of nanoparticles and metal-organic gel samples are analyzed using a Rigaku Smart Lab diffractometer with a Cu-Kα light source (ca. 1.541 Å); Diffraction data are collected at 2θ angles from about 2° to about 30°, a gap size of about 0.01°, and a step rate of about 1°/min.

Test example 5: Atomic force microscopy: AFM ) analyze

Atomic force microscopy (AFM) height topography and AM-FM amplitude modulated-frequency modulated tapping mode imaging are performed in air using the Asylum Research MFP-3D AFM. A Silicon AFM probe (Tap300-G, Budget Sensor) with a resonance frequency of approximately 300 kHz and a force constant of approximately 40 N/m attached to an AM-FM cantilever holder was used to measure nanomechanical properties. do; Tip calibration is performed using a standard sample of Matrimid® 5218 with Young's modulus set to approximately 4 GPa.

Test example 6: Electrical conductivity test

The electrical conductivity of metal-organic gel samples is measured using a Keithley 2614B sourcemeter and a custom-made conductive cell with aluminum electrodes placed approximately 1 cm apart. The settings for measuring the electrical conductivity are shown in FIG. 23.

The conductivity of viscoelastic solids is measured on a thin film of ACN viscoelastic material placed between a pair of flat aluminum electrodes.

Although the preferred embodiments have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept defined in the following claims are also within the scope of the present invention. It belongs.

Claims (20)

Supramolecular Metal-Organic Framework Material in a gel state, which is a reaction product of a copper compound, a trialkylamine represented by the following formula (1), and benzene substituted with three or more carboxyl groups:
[Formula 1]

In Formula 1,
R ¹ , R ² and R ³ are the same or different from each other and are each independently a C1 to C10 alkyl group. In claim 1, the copper compound is copper nitrate (Cu(NO ₃ ) ₂ ), the trialkylamine represented by Formula 1 is triethylamine (NEt ₃ ), and the benzene substituted with 3 or more carboxyl groups is 1. ,3,5-Benzenetricarboxylic acid (BTC), a gel-like supramolecular metal-organic structure material. In claim 1, the reaction is carried out in a non-aqueous organic solvent, a supramolecular metal-organic structure material in a gel state. In claim 3, the non-aqueous organic solvent is C1-C10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), N,N -Dimethylacetrimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methyl ethyl ketone (MEK), pyridine, or a combination thereof, a supramolecular metal-organic structure in a gel state. matter. delete delete A viscoelastic supramolecular metal-organic framework material obtained from the gel-state supramolecular metal-organic framework material according to any one of claims 1 to 4. A supramolecular metal-organic framework material in the form of nanoparticles, obtained from the gel-state supramolecular metal-organic framework material according to any one of claims 1 to 4. A supramolecular metal-organic framework material having a lamella structure, obtained from the gel-state supramolecular metal-organic framework material according to any one of claims 1 to 4. It involves reacting a copper compound, a trialkylamine represented by the following formula (1), and benzene substituted with three or more carboxyl groups in a non-aqueous organic solvent, wherein the copper compound is copper nitrate (Cu(NO ₃ ) ₂ ), Method for manufacturing gel-like supramolecular metal-organic framework material:
[Formula 1]

In Formula 1,
R ¹ , R ² and R ³ are the same or different from each other and are each independently a C1 to C10 alkyl group. In claim 10, the trialkylamine represented by Formula 1 is triethylamine (NEt ₃ ), and the benzene substituted with three or more carboxyl groups is 1,3,5-benzenetricarboxylic acid (BTC). Method for producing supramolecular metal-organic structure materials. In claim 10, the non-aqueous organic solvent is C1-C10 alkanol, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF), N,N -Dimethylacetrimide (DMAc), acetonitrile (ACN), toluene, dioxane, chlorobenzene, methyl ethyl ketone (MEK), pyridine, or a combination thereof, a supramolecular metal-organic structure in a gel state. Method of manufacturing the substance. In claim 10, the non-aqueous organic solvent is methanol, ethanol, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), acetonitrile (ACN), or a mixture thereof, supramolecular metal in a gel state. -Method for manufacturing organic structure materials. delete In claim 10, the reaction is performed by reacting a solution containing the copper compound and a solution containing the trialkylamine represented by Formula 1 with benzene substituted with three or more carboxyl groups to obtain a product, and the obtained product A method for producing a supramolecular metal-organic structure material in a gel state, comprising applying heat to or leaving it for a certain period of time. A solution containing a copper compound and a solution containing benzene substituted with three or more carboxyl groups are reacted with a trialkylamine represented by the following formula (1) to obtain a product, and the obtained product is heated or left for a certain period of time. After preparing a gel-like material, it includes leaving the gel-like material for a certain period of time, wherein the copper compound is copper nitrate (Cu(NO ₃ ) ₂ ), a viscoelastic supramolecular metal- Method for manufacturing Supramolecular Metal-Organic Framework Material:
[Formula 1]

In Formula 1,
R ¹ , R ² and R ³ are the same or different from each other and are each independently a C1 to C10 alkyl group. A solution containing a copper compound and a solution containing benzene substituted with three or more carboxyl groups are reacted with a trialkylamine represented by the following formula (1) to obtain a product, and the obtained product is heated or left for a certain period of time. A supramolecular metal-organic structure material in the form of nanoparticles, comprising preparing a gel-like material and then drying the gel-like material, wherein the copper compound is copper nitrate (Cu(NO ₃ ) ₂ ). Manufacturing method of (Supramolecular Metal-Organic Framework Material):
[Formula 1]

In Formula 1,
R ¹ , R ² and R ³ are the same or different from each other and are each independently a C1 to C10 alkyl group. A molded article comprising the gel-like supramolecular metal-organic framework material according to any one of claims 1 to 4. The molded article of claim 18, wherein the molded article is a film. An electronic device comprising a molded article according to claim 19.

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