KR102048115B1 - Covalent organic framework - Google Patents

Abstract

상기 화학식 1에서, A는 C, N, P, 또는 S이고, p1과 p2은 서로에 관계없이 1 또는 2의 정수이고, q1과 q2은 서로에 관계없이 0 또는 1의 정수이고, n은 0 또는 1의 정수일 수 있다. 다만, n이 0인 경우에는 A는 C가 아니다.Provided is a covalently bonded organic framework comprising a multidentate ligand as a unit. The organic framework may have a triazine group formed through nitrile trimerization of units represented by the following Chemical Formula 1.
[Formula 1]

In Formula 1, A is C, N, P, or S, p1 and p2 are integers of 1 or 2 irrespective of each other, q1 and q2 are integers of 0 or 1 irrespective of each other, n is 0 Or an integer of 1. However, when n is 0, A is not C.

Description

Covalent Organic Framework {Covalent organic framework}

The present invention relates to an organic framework, and more particularly, to an organic framework formed by covalent bonds.

Zeolite is a generic term for crystalline aluminosilicates, and zeolites obtainable in nature from ancient times have been used as water softeners. However, in the 1950s, after zeolites formed a structure different from natural products from an alkaline reactant through a hydrothermal reaction, research on industrial use of the structure became active. Furthermore, much research has been made in the field of adsorbents and catalysts, as the crystal structure of the zeolite is revealed and the pore size allows the selective adsorption of molecules of different sizes.

Due to the various advantages of these microporous materials, studies on various synthesis methods of zeolites have been conducted, and organic structures having similar physical properties have been rapidly researched. Among them, metal organic structures (ex. KR 2016-0005218) are most representative. to be.

Metal organic framework (MOF) is a structure that sets transition metal ions or metal clusters as the center of three-dimensional structure formation and connects various organic ligands through coordination bonds. However, such a metal organic structure is vulnerable to moisture as it contains a metal has a disadvantage that the three-dimensional structure quickly collapses when exposed to air. In addition, such a metal organic structure has a disadvantage of being vulnerable to heat.

Accordingly, the problem to be solved by the present invention is to provide an organic framework that is stable against moisture and heat.

Technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above technical problem, an aspect of the present invention provides an organic framework. The organic framework may have a triazine group formed through nitrile trimerization of units represented by Formula 1 below.

[Formula 1]

In Formula 1, R _a1 and R _a2 may be hydrogen. R _b1 , R _b2 , R _b3 , and R _b4 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group, an alkyl carboxylate group, Or a phenyl group, R _b1 and R _b2 may form a benzene ring fused to the parent to which they are attached, or R _b3 and R _b4 may form a benzene ring fused to the parent to which they are attached. R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group , An alkylcarboxylate group, or a phenyl group, R _c2 and R _c3 may form a benzene ring fused to the parent to which they are attached, or R _d2 and R _d3 may form a benzene ring fused to the parent to which they are attached have. A is C, N, P, or S, p1 and p2 are integers of 1 or 2, regardless of each other, g1 and g2 are integers of 0 or 1, regardless of each other, and n can be an integer of 0 or 1 have. However, when n is 0, A is not C.

The unit may be a unit represented by the following Formula 2A or 2B.

[Formula 2A]

[Formula 2B]

In Formula 2A or 2B, R _b1 , R _b2 , R _b3 , R _b4 , R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 , and A are the same as in Formula 1.

It may further include a transition metal chelated by the unit of Formula 1. The transition metal is at least one selected from the group consisting of Ir, Pd, Pt, Mo, Fe, Co, Ni, Ru, Rh, Re, Au, Cr, Ag, W, Zn, Al, Mn, Ti and Pd It may be a metal.

The organic framework may be formed through nitrile trimerization of the units represented by Formula 1 and the linkers represented by Formula 4 below.

[Formula 4]

In Formula 4, R _e1 , R _e2 , R _e3 , R _e4 , R _f1 , R _f2 , R _f3 , and R _b4 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, A nitro group, an amine group, a halogen group, a carboxyl group, an alkylcarboxylate group, or a phenyl group, or a pair of R _e1 and R _e2 , a pair of R _e3 and R _e4 , a pair of R _f1 and R _f2 , and R _f3 and The pair of R _f4 irrespective of each other forms a benzene ring fused to the parent to which they are attached, and m can be an integer of 0 or 1.

Another aspect of the present invention to achieve the above technical problem provides a method for producing an organic skeleton. First, the units represented by Chemical Formula 1 are provided. The units are heated in an ionic liquid to carry out a nitrile trimerization reaction.

The heating temperature may be 250 to 500 ℃. The ionic liquid may be ZnCl 2.

In order to achieve the above technical problem, another aspect of the present invention provides a gas collector having the organic framework. At this time, the gas collected may be carbon dioxide.

In order to achieve the above technical problem, another aspect of the present invention provides a catalyst composition having the organic framework.

As described above, according to the present invention, the organic framework may have a porous structure. This porous structure allows organic frameworks to trap gases.

Furthermore, the organic framework has carbon dioxide as well as having a porous structure, a triazine group, and a heterocyclic aromatic ring having N, P, or S together with a pair of carbine groups or one carbine group in a unit. Adsorption efficiency of can be greatly improved. As a result, the selective adsorption efficiency of carbon dioxide on nitrogen can be improved. Such an organic framework can selectively absorb carbon dioxide from the exhaust gas of a factory or a vehicle, thereby preventing it from being released into the air, and thus may be used as a carbon dioxide collector.

The organic framework can stably fix the transition metal by chelating the transition metal used as a catalyst.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 illustrates a structure of an organic framework unit layer according to an embodiment of the present invention.
2 illustrates a structure of an organic framework unit layer according to another embodiment of the present invention.
3 shows an exemplary structure of an organic framework unit layer according to another embodiment of the present invention.
4 is an X-ray diffraction graph of the covalently bonded organic framework powder obtained in Preparation Examples 1 to 4.
5 shows the results of EDS analysis of the covalently bonded organic framework particles obtained in Preparation Example 1. FIG.
6 shows FT-IR spectroscopic graphs of organic frameworks according to Preparation Examples 1-4.
7 shows a solid state CPMAS ¹³ C-NMR spectral graph of the organic framework according to Preparation Examples 1-4.
FIG. 8 is a graph showing thermal gravimetric analysis (TGA) results of organic frameworks and monomers according to Preparation Examples 1 to 4. FIG.
FIG. 9 is a graph illustrating an isothermal adsorption-desorption graph (a) and pore diameter distribution of organic frameworks according to Preparation Examples 2 to 4 (b).
FIG. 10 is a graph illustrating an isothermal adsorption-desorption graph (a) of the organic frameworks according to Preparation Examples 2 to 4 and a graph (b) illustrating adsorption heat with respect to the amount of CO 2 absorbed.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to describe the present invention in more detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. In the figures, where a layer is said to be "on" another layer or substrate, it may be formed directly on the other layer or substrate, or a third layer may be interposed therebetween.

In the present specification, when "X to Y" is described, the number corresponding to all integers between X and Y should be interpreted as being described together.

As used herein, "alkyl" means an aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds. Alternatively, the alkyl group may be an "unsaturated alkyl group" containing at least one double bond or triple bond. The alkyl group, whether saturated or unsaturated, may be branched, straight chain or cyclic. The alkyl group may be an alkyl group having 1 to 6 carbon atoms. More specifically, the alkyl group may be selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl.

As used herein, "halo" or "halogen" is F, Cl, Br, or I unless otherwise defined. Specifically, it may be F, Cl, or Br.

Covalent organic framework

An organic framework according to an embodiment of the present invention may be formed through nitrile trimerization of units represented by the following Formula 1.

[Formula 1]

In Formula 1, R _a1 and R _a2 may be hydrogen.

R _b1 , R _b2 , R _b3 , and R _b4 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group, an alkyl carboxylate group, Or a phenyl group, or R _b1 and R _b2 form an aromatic ring fused to the parent to which they are attached, eg, a benzene ring, or R _b3 and R _b4 form an aromatic ring fused to the parent to which they are attached, It can form a benzene ring.

R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group , An alkyl carboxylate group, or a phenyl group. Or R _c2 and R _c3 form an aromatic ring fused to the parent to which they are attached, eg a benzene ring, or R _d2 and R _d3 form an aromatic ring fused to the parent to which they are attached, eg a benzene ring Can be formed.

A can be C, N, P or S. p1 and p2 may be integers of 1 or 2 irrespective of each other, g1 and g2 may be integers of 0 or 1 irrespective of each other, and n may be an integer of 0 or 1. However, when n is 0, A is not C.

The monomer represented by the formula (1) has nitrile groups at each end. When these units are adjacent to each other in the polymerization process, the terminal nitrile groups of the adjacent units may be trimerized to form an organic framework. Such organic frameworks may have a porous structure. This porous structure allows the organic framework to physically adsorb gases, in particular carbon dioxide or nitrogen.

Meanwhile, imidazolium in the unit represented by Chemical Formula 1 may form a carbene having a neutral carbon atom having a lone pair in the resonance process. Furthermore, the unit has two carbine groups adjacent to each other in its molecular structure (n = 1), or one carbine group (n = 0), wherein A has N, P having a non-covalent electron pair, not C. Or S. In addition, the unit has a triazine formed by trimerization of tril. The interaction between the unshared electron pair of the carbin group, the unshared electron pair when A is N, P, or S, and the unshared electron pair of N of triazine and carbon of carbon dioxide can further improve the adsorption efficiency of carbon dioxide.

As described above, the organic framework according to the present embodiment has a heterocyclic aromatic ring having N, P, or S together with a triazine group and a pair of carbine groups or one carbine group in addition to the porous structure. By providing a carbon dioxide adsorption efficiency can be greatly improved. As a result, the selective adsorption efficiency of carbon dioxide on nitrogen can be improved. Such an organic framework can selectively absorb carbon dioxide from the exhaust gas of a factory or a vehicle, thereby preventing it from being released into the air, and thus may be used as a carbon dioxide collector.

In addition, carbines can form very strong coordination bonds to transition metals as σ-donor ligands. Thus, when one unit has two adjacent carbine groups or one carbine group and has a heterocyclic aromatic ring having N, P, or S adjacent thereto, the unit has several Site ligands, in other words, can chelate metals to stably fix transition metals in the organic framework.

At this time, the transition metal fixed in the organic framework can further increase the adsorption efficiency of carbon dioxide in the organic framework. The transition metal is at least one selected from the group consisting of Ir, Pd, Pt, Mo, Fe, Co, Ni, Ru, Rh, Re, Au, Cr, Ag, W, Zn, Al, Mn, Ti and Pd It may be a metal. In addition, such transition metals can also serve as catalysts, so that the organic framework can enable efficient catalysis in its pores. Such organic frameworks can be catalysts (when a transition metal is included) or catalyst carriers (when a transition metal is not included). In other words, the organic framework can be contained in a catalyst composition.

In the case of having two carbin groups adjacent to each other in one unit, it may be represented by the following formula (2A).

[Formula 2A]

In Formula 2A, R _b1 , R _b2 , R _b3 , R _b4 , R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 , and A are as described in Formula 1.

A case where an aromatic ring containing A (= N, P, or S) having one carbin group and an unshared electron pair adjacent thereto is included in one unit may be represented by the following Chemical Formula 2B.

[Formula 2B]

In Formula 2B, R _b1 , R _b2 , R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 , and A are as described in Formula 1.

Specific examples of such a unit may be represented by the following Chemical Formulas 3A to 3I.

[Formula 3A]

[Formula 3B]

[Formula 3C]

[Formula 3D]

[Formula 3E]

[Formula 3F]

[Formula 3G]

[Formula 3H]

Formula 3I]

The basic unit structure of the unit 3A formed by nitrile insertion may be represented by Structural Formula 1 below.

[Formula 1]

Referring to Structural Formula 1, when three units 3A are adjacent to each other, three nitrile groups included in each of the end groups may be trimerized to form a triazine group. Furthermore, FIG. 1 shows an exemplary structure of an organic framework unit layer having the unit structures of Structural Formula 1 above.

The basic unit structure of the monomer 3D formed by nitrile insertion may be represented by the following Structural Formula 2.

[Formula 2]

Referring to Structural Formula 2, when three unit 3Ds are adjacent to each other, three nitrile groups included in the respective end groups may be trimerized to form triazine groups. 2 shows an exemplary structure of an organic framework unit layer having the unit structures of Structural Formula 2 above.

The preparation of the organic framework can be carried out using ionothermal synthesis using an ionic liquid as the reaction medium. The ionic liquid may be, for example, ZnCl ₂ . When the ion-thermal synthesis method is performed, the reaction temperature may be about 200 to 550 ° C, for example, 250 to 500 ° C. When the reaction temperature increases, for example, at a temperature of 400 ° C. or higher, triazine groups in the organic framework may be pyrolyzed to cause graphitization. As a result, the surface area may be increased to increase the collection efficiency of the gas including CO 2. However, in order to enhance the selective capture of carbon dioxide to nitrogen due to the remaining of the triazine group to some extent with an appropriate increase in surface area, an appropriate reaction temperature of the ion-thermal synthesis method may be 350 to 450 ° C. The time for performing the ion-thermal synthesis method may be about 30 to 120 hours.

The unit layers shown in each of FIGS. 1 and 2 may be two-dimensionally expanded porous graphitic layers, and the organic framework may have a structure in which the unit layers are stacked. In the layered structure, the unit layers may have non-covalent interaction, specifically, pi interaction, so that corresponding pores in a plurality of unit layers adjacent to each other in the layered structure are not randomly disposed. It can be arranged in alignment. In this case, pores penetrating the plurality of unit layers may be formed. In this case, a polycrystalline structure may be created that at least partially represents a three-dimensional crystal structure. However, the present invention is not limited thereto, and corresponding pores in the plurality of unit layers may be randomly disposed to form an amorphous structure.

The organic framework according to another embodiment of the present invention may be formed through nitrile trimerization of the monomers represented by Formula 1 and the linkers represented by Formula 4 below. For example, the unit represented by Chemical Formula 1 and the linkers represented by Chemical Formula 4 may be present in the organic framework in a molar ratio of 1: 1 to 1: 5.

[Formula 4]

In Chemical Formula 4,

R _e1 , R _e2 , R _e3 , R _e4 , R _f1 , R _f2 , R _f3 , and R _b4 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a methoxy group, a nitro group, an amine group , A halogen group, a carboxyl group, an alkylcarboxylate group, or a phenyl group, or a pair of R _e1 and R _e2 , a pair of R _e3 and R _e4 , a pair of R _f1 and R _f2 , and a pair of R _f3 and R _f4 Regardless, they can form aromatic rings, for example benzene rings, fused to the parent to which they are attached.

m may be an integer of 0 or 1.

The linker represented by Formula 4 may be represented by the following Formula 5A or 5B.

[Formula 5A]

[Formula 5B]

The basic unit structure formed by the linker represented by Formula 5A by nitrile insertion may be represented by the following Structural Formula 3.

[Formula 3]

The basic unit structure formed by the linker represented by Formula 5B by nitrile insertion may be represented by the following Structural Formula 4.

[Structure 4]

3 illustrates an exemplary structure of an organic framework unit layer including the unit structures of Formula 1 and the unit structures of Formula 3. In FIG. 3, the organic framework unit layer shows that the unit structures of Structural Formula 1 and the unit structures of Structural Formula 3 are regularly arranged, but is not limited thereto and may be irregularly arranged in at least a portion of the organic framework unit layer. It may be.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Covalent organic Skeletal body Production Example  One

1-methylimidazole and 2-bromo-5-cyanopyridine were put in a sealed pressure tube and heated to 190 ° C. for 18 hours, and 1,3- Bis (5-cyanopyridyl) imidazolium bromide (1,3-bis (5-cyanopyridyl) imidazolium bromide; bpim) was obtained as a grayish crude powder. The filtrate obtained by pouring hot methanol into this powder was cooled to room temperature to obtain light brown needles.

The crystals were placed in a closed glass ampoule and heated to 250 ° C. for 48 hours under ionothermal conditions using ZnCl ₂ as a solvent and Lewis acid catalyst to obtain a covalent organic framework as a black powder.

Preparation Example 2 of Covalent Organic Framework

The covalently bonded organic framework was obtained as black powder by the same method as Preparation Example 1, except that the ionic thermal synthesis was performed at 300 ° C instead of 250 ° C.

Preparation Example 3 of Covalent Organic Framework

The covalently bonded organic framework was obtained as black powder by the same method as Preparation Example 1, except that the ionic thermal synthesis was performed at 400 ° C instead of 250 ° C.

Preparation Example 4 of Covalent Organic Framework

A covalently bonded organic framework was obtained as black powder by the same method as Preparation Example 1, except that the ion-thermal synthesis was performed at 500 ° C instead of 250 ° C.

4 is an X-ray diffraction graph of the covalently bonded organic framework powder obtained in Preparation Examples 1 to 4.

Referring to FIG. 4, it can be seen that 2θ represents a broad peak when it is near 25 °. This peak may be attributed to the (001) plane in the framework. Therefore, it can be seen that the covalently bonded organic framework powders obtained in Production Examples 1 to 4 have a graphite 2D structure but are generally an amorphous structure. On the other hand, considering that 2θ is 25 °, the interlayer distance between the graphite 2D structures may be about 3.6 kW.

Table 1 below shows the results of elemental analysis (EA) analysis of the covalently bonded organic framework powders obtained in Preparation Examples 1 to 4.

C
(wt%) N
(wt%) H
(wt%) C / N C / N
Theoretical value Monomer 48.77 22.58 3.04 2.16 2.14 Preparation Example 1 56.76 26.03 3.75 2.17 2.14 Preparation Example 2 52.46 22.09 4.19 2.37 2.14 Preparation Example 3 53.4 18.77 4.16 2.84 2.14 Preparation Example 4 48.42 14.51 4.52 3.34 2.14 Monomer: 1,3-bis (5-cyanopyridyl) imidazolium bromide (bpim)

Referring to Table 1, the organic framework according to Preparation Example 1 has a C / N ratio of 2.17, which is similar to the C / N ratio of monomer 2.16 and the theoretical C / N ratio of 2.14 in the organic framework. The organic frameworks thus appeared to exhibit minimal compositional changes. However, the organic framework obtained by ion-thermal synthesis at 500 ° C. significantly increased the C / N ratio to 3.337, which can be estimated to be gradually graphitized as the synthesis temperature increases.

5 shows the results of EDS analysis of the covalently bonded organic framework particles obtained in Preparation Example 1.

Referring to FIG. 5 and Table 1, it can be seen that Cl is evenly distributed in the framework particles at low intensities of about 1 at.% Or less. From this, it can be predicted that a stable bond has been formed between the Cl anion and the counterion in the bpim functional group, from which it can be assumed that the bpim functional group was successfully incorporated into the triazine-based framework.

6 shows FT-IR spectroscopic graphs of organic frameworks according to Preparation Examples 1-4.

Referring to FIG. 6, since the organic framework does not show a peak at 2200 cm ⁻¹ related to CN stretching relative to bpim, the nitrile groups of bpim may be estimated to be completely converted to triazine. On the other hand, the peaks seen at 1450-1600 cm ⁻¹ (C = N or C = C), 1200-1400 cm ⁻¹ (CN or CC), and 800-850 cm ⁻¹ (heterocyclic aromatic) are somewhat broadened and merged Form, which may be evidence for triazine, pyridine, and imidazolium moieties. On the other hand, as the synthesis temperature increases, the IR spectrum widens and the peaks become indistinguishable, which can be understood as the collapse of the skeletal part and the graphitization by the increase in temperature.

7 shows a solid state CPMAS ¹³ C-NMR spectral graph of the organic framework according to Preparation Examples 1-4.

Referring to FIG. 7, no signal of nitrile group was observed in the region of 100-110 ppm, meaning that all nitriles were converted to triazine. In addition, a signal of 169 ppm was assigned to triazine, and can be clearly seen in the spectral graph of the organic framework (bpim-CTF-250) according to Preparation Example 1. On the other hand, some signals appeared at 115 at 131, 150 and 155-160 ppm, which are due to the pyridine groups substituted with imidazolium groups. In particular, the signal of C2 carbon in the imidazolium cation is clearly detected at 137 ppm, which is in good agreement with the peak position of the monomer.

On the other hand, the intensity of the triazine peak at 169 ppm is significantly decreased when the ion-heat synthesis temperature reaches 300 degrees (bpim-CTF-300), and is almost invisible at 400 degrees (bpim-CTF-400). It can be assumed that the group is pyrolyzed when the ion-thermal synthesis temperature is increased. Nevertheless, the signal of the pyridine group in the region of 120-160 ppm appears to be maintained, although the intensity decreases with increasing ion-thermal synthesis temperature. In particular, the signal of C2 carbon of imidazolium appears to exist in the structure up to 400 degrees. This can be confirmed that Cl is stably present in the framework as a counter ion up to 400 degrees of ionic heat synthesis temperature, as shown in the EDS results shown in Table 1.

As such, it was shown that pyridine and imidazolium exist in the organic framework when the ionic heat synthesis temperature is 250 to 500 degrees, but the triazine is completely pyrolyzed when it reaches 500 degrees.

FIG. 8 is a graph showing thermal gravimetric analysis (TGA) results of organic frameworks and monomers according to Preparation Examples 1 to 4. FIG.

Referring to FIG. 8, it can be seen that the organic frameworks maintain the total weight up to about 300 ° C. except for the weight loss due to the evaporation of water at 100-120 ° C. FIG. However, above 300 ° C, a gradual weight loss occurs, which can be seen as a result of partial decomposition of the local structure. Nevertheless, compared to the monomer bpim, more than 80% of the weight of the organic framework is maintained at about 500 degrees or more, which is attributed to the rich aromatic systems that provide strong covalent bonds in the framework. . This shows that the heat resistance characteristics of the organic frameworks according to Preparation Examples 1 to 4 are excellent.

Table 2 below shows various physical properties of the organic frameworks according to Preparation Examples 2 to 4.

BET
Surface area
[m ² g ^-1 ] CO ₂ uptake
[mmolg ^-1 ] N ₂ uptake
[mmolg ^-1 ] Total pore
volume
[cm ³ g ^-1 ] Micropore volume
[cm ³ g ^-1 ] Mesopore volume
[cm ³ g ^-1 ] Qst
[kJmol ^-1 ] Selectivity
IAST 288K 298K max min Preparation Example 2 2.4 0.29 0.28 0.04 0.0057 0.0018 0.0039 - - - Preparation Example 3 786 2.85 2.46 0.20 0.3436 0.3362 0.0074 31 27 32 Preparation Example 4 1556 3.31 2.77 0.25 0.7541 0.7394 0.0147 28 25 23.5

FIG. 9 is a graph illustrating an isothermal adsorption-desorption graph (a) and pore diameter distribution of organic frameworks according to Preparation Examples 2 to 4 (b).

9 and Table 1, as a result of isothermal N2 adsorption and desorption measurement at 77 K, the organic framework at ionic thermosynthesis temperature of 250 degrees (bpim-CTF-250, Preparation Example 1) and the organic framework at 300 degrees (bpim-CTF-300, Preparation Example 2) was such that N2 adsorption was negligible. However, it can be seen that the adsorption of N 2 is significantly increased when the ion thermosynthesis temperature is increased. When the ion thermosynthesis temperature is 400 degrees (bpim-CTF-400, Preparation Example 3), the N2 adsorption tendency follows the typical form of isotherm type I, which exhibits a fast adsorption capacity at low relative pressures (P / P ₀ <0.05). Appeared. This may mean the presence of micro pores in the framework. On the other hand, when the ion thermosynthesis temperature was 500 degrees (bpim-CTF-500, Preparation Example 4), the N2 isotherm was shifted and saturated at a relatively high pressure (P / P ₀ > 0.3). This may mean that wider-sized micropores have been created in the framework at high synthesis temperatures.

This interpretation can be supported by the pore size distribution by the Non-Local Density Functional Theory (NLDFT) calculation. Specifically, when the ion thermosynthesis temperature is 300 degrees (bpim-CTF-300, Preparation Example 2), the narrow peak was 0.6 nm, indicating that the dominant pores were ultra-micropores (d <0.7 nm). Can mean. Therefore, when the ionic thermosynthesis temperature is 250 degrees (bpim-CTF-250, Preparation Example 1) and 300 degrees (bpim-CTF-300, Preparation Example 2), N2 adsorption degree of negligible N2 is ultra- It may be due to the difficult diffusion in the microporous system. However, when the synthesis temperature is increased, that is, when the ion thermosynthesis temperature is 400 degrees (bpim-CTF-400, Preparation Example 3) and 500 degrees (bpim-CTF-500, Preparation Example 4), it is 1 nm as a slightly wider peak. And 1-1.6nm, respectively, which may mean that the pore size distribution is shifted to a micropore system (1-2nm). Therefore, it can be understood that as the synthesis temperature increases, the pore size becomes wider and the formation of irregularly sized pores can be promoted. As a result, the BET surface area (BET SA) in the organic framework was 786 m, respectively, when the ionic thermosynthesis temperature was 400 degrees (bpim-CTF-400, Preparation Example 3) and 500 degrees (bpim-CTF-500, Preparation Example 4). ² g ^-1 and 1556m ² g ^-1 , more than 97% of which was interpreted as being due to micropore volume.

FIG. 10 is a graph illustrating CO 2 isothermal adsorption-desorption graph (a) of organic frameworks according to Preparation Examples 2 to 4 and a graph (b) illustrating adsorption heat with respect to the amount of CO 2 absorbed.

10 and Table 2, for the analysis of CO2 absorption capacity, isothermal adsorption and desorption measurements were performed at 288 and 298 K up to 1 bar, with an ion thermosynthesis temperature of 500 degrees (bpim-CTF-500, In Preparation Example 4), the CO 2 absorption volume by the organic framework showed a remarkable amount of CO 2 absorption and adsorption, such as 3.31 mmol at 288K and 2.77 mmol at 298K.

On the other hand, the heat of adsorption (Qst), a parameter representing the affinity between CO 2 and the porous adsorbent, is 31 kJmol ^-1 at zero coverage in the case of the organic framework (bpim-CTF-400, Preparation Example 3) having an ionic thermosynthesis temperature of 400 degrees. It was reduced to 27 kJmol ^-1 when adsorbed. In comparison, in the case of the organic framework (bpim-CTF-500, Preparation Example 4) having an ion thermosynthesis temperature of 500 degrees, the heat of adsorption showed 28 kJmol ^-1 at zero coverage and decreased to ²⁵ kJmol ^-1 when adsorbed. . This heat of adsorption was determined to fall within the 30-50 kJmol ^-1 region where adsorption and desorption of CO 2 occurred effectively in a carbon capture and storage (CCS) operation. In particular, the overall heat of adsorption is the organic framework (bpim-CTF-400, Preparation Example 3) having an ion thermosynthesis temperature of 400 degrees, and the organic framework (bpim-CTF-500, Preparation Example 4) having an ion thermosynthesis temperature of 500 degrees. It was larger than in the case due to the high abundance of functional groups due to low graphitization.

Given that 80% of the fuel emissions are N2, 15% CO2, 3% H2O and the rest are other contaminants, selective absorption and subsequent removal of CO2 can increase the potential for practical use for CCS. Ion thermosynthesis with an organic framework (bpim-CTF-400, Preparation Example 3) with an ion thermosynthesis temperature of 400 degrees, obtained using IAST (ideal adsorbed solution theory) under CO2: N2 (0.15: 0.85) at 298K CO2 / N2 adsorption selectivity of the organic framework (bpim-CTF-500, Preparation Example 4) with a temperature of 500 degrees was 32 and 23.5, respectively.

As such, it can be seen that the temperature of the appropriate ion-thermal synthesis for the selective adsorption of carbon dioxide to nitrogen is around 400 degrees.

Covalent organic Skeletal body Production Example  5

1 mole equivalent of 1,3-bis (5-cyanopyridyl) imidazolium bromide (1,3-bis (5-cyanopyridyl) imidazolium bromide (bpm)) and tetraphthalonitrile (terephthalonitrile) as light brown needles 1) 1 molar equivalent of linker was placed in a closed glass ampoule and heated for 48 hours at 250 ° C. under ionothermal conditions using ZnCl ₂ as a solvent and Lewis acid catalyst to form a covalent organic framework as a black powder. Got it.

Preparation Example 6 of Covalent Organic Framework

Except for using 5 molar equivalents of linker 1, the same method as in Preparation Example 5 was carried out to obtain a covalent organic framework as a black powder.

Covalent organic Skeletal body Production Example  7

1 mole equivalent of 1,3-bis (5-cyanopyridyl) imidazolium bromide (1,3-bis (5-cyanopyridyl) imidazolium bromide; bpim), a light brown needle, and [1,1'- 1 molar equivalent of biphenyl] -4,4'-dicarbonitrile ([1,1'-biphenyl] -4,4'-dicarbonitrile, linker 2) is placed in a closed glass ampoule and ZnCl ₂ is added to the solvent and Lewis acid catalyst. The mixture was heated at 250 ° C. for 48 hours under ionothermal conditions to obtain a covalent organic framework as a black powder.

Preparation Example of Covalent Organic Framework

Except for using 5 molar equivalents of linker 2, the same method as in Preparation Example 7 was carried out to obtain a covalent organic framework as a black powder.

In Table 3 below, the BET surface area, total pore volume, and average pore diameter of the organic frameworks according to Preparation Examples 5 to 8 were measured.

bpim: linker
Molar ratio BET
Surface area
[m ² g ^-1 ] Total pore
volume
[cm ³ g ^-1 ] Average pore
diameter
[cm ³ g ^-1 ] Preparation Example 5 1: 1 837.72 0.4847 2.2153 Preparation Example 6 1: 5 2597.5 1.438 2.2144 Preparation Example 7 1: 1 875.2 0.4711 2.2492 Preparation Example 8 1: 5 1084 0.5995 2.2121

Referring to Table 3, Preparation Examples 5 to 8 all showed nearly similar average pore diameters. However, when the molar ratio of the linker increases, the BET surface area and the total pore volume increase significantly.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. This is possible.

Claims (15)

An organic framework having triazine groups formed through nitrile trimerization of units represented by Formula 1 and linkers represented by Formula 4 below:
[Formula 1]

[Formula 4]

In Chemical Formula 1,
R _a1 and R _a2 are hydrogen,
R _b1 , R _b2 , R _b3 , and R _b4 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group, an alkyl carboxylate group, Or a phenyl group, R _b1 and R _b2 form a benzene ring fused to the parent to which they are attached, or R _b3 and R _b4 form a benzene ring fused to the parent to which they are attached,
R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group , An alkylcarboxylate group, or a phenyl group, R _c2 and R _c3 form a benzene ring fused to the parent to which they are attached, or R _d2 and R _d3 form a benzene ring fused to the parent to which they are attached,
A is C, N, P, O, or S,
p1 and p2 are integers of 1 or 2, independent of each other,
g1 and g2 are integers of 0 or 1 irrespective of each other,
n is an integer of 0 or 1, except that when n is 0, A is not C,
In Chemical Formula 4,
R _e1 , R _e2 , R _e3 , R _e4 , R _f1 , R _f2 , R _f3 , and R _b4 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a methoxy group, a nitro group, an amine group , A halogen group, a carboxyl group, an alkylcarboxylate group, or a phenyl group, or a pair of R _e1 and R _e2 , a pair of R _e3 and R _e4 , a pair of R _f1 and R _f2 , and a pair of R _f3 and R _f4 Regardless of each other, they form a benzene ring fused to the parent to which they are attached,
m is an integer of 0 or 1. The method of claim 1,
The monomer represented by Formula 1 is an organic skeleton that is a unit represented by Formula 2A:
[Formula 2A]

In Formula 2A, R _b1 , R _b2 , R _b3 , R _b4 , R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 , and A are the same as in Formula 1. The method of claim 1,
The monomer represented by Formula 1 is an organic skeleton that is a unit represented by Formula 2B:
[Formula 2B]

In Formula 2B, R _b1 , R _b2 , R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 , and A are the same as in Formula 1. The method of claim 1,
The monomer represented by Formula 1 is an organic skeleton which is a unit represented by any one of the following Formulas 3A to 3I:
[Formula 3A]

[Formula 3B]

[Formula 3C]

[Formula 3D]

[Formula 3E]

[Formula 3F]

[Formula 3G]

[Formula 3H]

Formula 3I]

The method of claim 1,
An organic framework further comprising a transition metal chelated by the unit of Formula 1. The method of claim 5,
The transition metal is at least one selected from the group consisting of Ir, Pd, Pt, Mo, Fe, Co, Ni, Ru, Rh, Re, Au, Cr, Ag, W, Zn, Al, Mn, Ti and Pd Organic frameworks that are metal. delete The method of claim 1,
The linker represented by Chemical Formula 4 is an organic framework represented by the following Chemical Formula 5A or Chemical Formula 5B:
[Formula 5A]

[Formula 5B]

Providing units represented by Formula 1 and linkers represented by Formula 4; And
A method for preparing an organic skeleton comprising heating nitrile trimerization reaction by heating the linkers together with the units in an ionic stone liquid:
[Formula 1]

[Formula 4]

In Chemical Formula 1,
R _a1 and R _a2 are hydrogen,
R _b1 , R _b2 , R _b3 , and R _b4 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group, an alkyl carboxylate group, Or a phenyl group, R _b1 and R _b2 form a benzene ring fused to the parent to which they are attached, or R _b3 and R _b4 form a benzene ring fused to the parent to which they are attached,
R _c1 , R _c2 , R _c3 , R _d1 , R _d2 , and R _d3 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a methoxy group, a nitro group, an amine group, a halogen group, a carboxyl group , An alkylcarboxylate group, or a phenyl group, R _c2 and R _c3 form a benzene ring fused to the parent to which they are attached, or R _d2 and R _d3 form a benzene ring fused to the parent to which they are attached,
A is C, N, P, or S,
p1 and p2 are integers of 1 or 2, independent of each other,
g1 and g2 are integers of 0 or 1 irrespective of each other,
n is an integer of 0 or 1, except that when n is 0, A is not C,
In Chemical Formula 4,
R _e1 , R _e2 , R _e3 , R _e4 , R _f1 , R _f2 , R _f3 , and R _b4 are independently of each other hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a methoxy group, a nitro group, an amine group , A halogen group, a carboxyl group, an alkylcarboxylate group, or a phenyl group, or a pair of R _e1 and R _e2 , a pair of R _e3 and R _e4 , a pair of R _f1 and R _f2 , and a pair of R _f3 and R _f4 Regardless of each other, they form a benzene ring fused to the parent to which they are attached,
m is an integer of 0 or 1. delete The method of claim 9,
The heating temperature is 250 to 500 ℃ organic skeleton manufacturing method. The method of claim 9,
Wherein the ionic liquid is ZnCl 2. The gas collector provided with the organic skeleton of any one of Claims 1-6. The method of claim 13,
Said gas is carbon dioxide. The catalyst composition provided with the organic skeleton of any one of Claims 1-6.

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