KR20230026964A - Polymer/amine-grafted metal-organic framework based carbon dioxide adsorbents - Google Patents

Abstract

The present invention relates to a carbon dioxide adsorbent, which contains: a metal-organic framework in which amine is introduced at an open metal site; and a hydrophobic polymer binder coated on the surface of the metal-organic framework. According to the present invention, the hydrophobic polymer binder is introduced into the amine-functionalized metal-organic framework for the hydrophobic polymer to cover the surface of the metal-organic framework, which blocks the access of moisture, and as a result, it is possible to provide the carbon dioxide adsorbent, capable of exhibiting excellent adsorption performance by maintaining structural stability under moisture conditions.

Description

Polymer/amine-grafted metal-organic framework based carbon dioxide adsorbents}

The present invention relates to a carbon dioxide adsorbent based on a metal-organic framework grafted with a polymer/amine.

There are various gases in indoor air. Among them, carbon dioxide is used as an indicator of indoor air pollution because it has a great effect on the human body. For example, as the concentration of carbon dioxide in indoor air increases, physical condition may worsen, such as feeling drowsy, or symptoms such as stiff shoulders, headaches, and dizziness may occur. In addition, studies have shown that the higher the concentration of carbon dioxide, the more movement during sleep, and the overall lowering of the quality of sleep. For this reason, many countries, including Korea, Japan, and the United States, set the recommended indoor carbon dioxide concentration standard at 1000 ppm or less.

While the concentration of carbon dioxide in the outdoor air is maintained at about 400 ppm, the concentration of carbon dioxide in an enclosed room can increase rapidly if ventilation is not frequently performed due to outdoor dust. The concentration of carbon dioxide in the city will exceed 2000 ppm, and the concentration in small spaces such as personal vehicles and express buses can change more rapidly. In addition, as a result of measurement in the living rooms of 10 apartments throughout Seoul, the concentration of carbon dioxide showed a concentration distribution of 600 to 1200 ppm regardless of sleeping, cooking, and ventilation times, and it has been reported that the maximum is 1600 ppm or more. Therefore, there is a need to develop a technology for adsorbing or removing high-concentration carbon dioxide present indoors.

As a conventional carbon dioxide removal technology, there was a wet scrubbing technology to remove carbon dioxide in the exhaust gas of the factory, but the carbon dioxide concentration in the exhaust gas is as high as about 15%, so when applied indoors where the carbon dioxide concentration is around 0.04% Performance degradation may occur, and since the carbon dioxide removal device for exhaust gas uses a liquid-based absorbent, it is difficult to apply it to home appliances.

On the other hand, Metal-Organic Frameworks (MOFs) are crystalline solids composed of coordination bonds between metals and ligands, and have the advantage of having a large surface area and controlling pores. Research is in progress, and it has also been reported that when an amine group is introduced into MOF, the adsorption capacity is dramatically improved through chemical bonding between the amine group and carbon atoms of carbon dioxide.

However, when MOF is exposed to indoor environments with high relative humidity (e.g., greater than about 60% RH) or humid environments with a large amount of moisture, such as water vapor, which accounts for 5 to 7% of flue gas, its structure collapses. However, it has been pointed out that carbon dioxide adsorption capacity may decrease due to deterioration of the bond with the amine group, and thus, the development of a new carbon dioxide adsorbent capable of maintaining structural stability from moisture is required.

Republic of Korea Patent Publication No. 10-2015-0007484

The present invention has been made to solve the above problems, and an object of the present invention is to provide a MOF-based carbon dioxide adsorbent capable of exhibiting excellent adsorption performance even in a humid environment with improved moisture stability.

The present invention, in order to solve the above problems,

metal-organic skeletons in which amines are introduced at open metal sites; and a hydrophobic polymer binder coated on the surface of the metal-organic framework.

According to the present invention, the hydrophobic polymer binder is polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS) and styrene- It may be at least one styrene-based resin selected from the group consisting of butadiene-rubber (SBR).

In this case, the weight ratio of the metal-organic framework and the styrene-based resin may be 6:4 to 8:2.

In addition, the hydrophobic polymer binder is at least one hydrophobic polymer material selected from the group consisting of polydimethylsiloxane (PDMS), polytetrafluoroethylene PTFE, and polyvinylidene fluoride (PVDF). can include more.

In this case, the weight ratio of the styrenic resin to the hydrophobic polymer material may be 1:1 to 1:3.

According to the present invention, the porous metal-organic framework is M ₂ (dobpdc), M ₂ (dobdc), M ₂ ( o -dobdc), M ₂ ( m -dobdc), M ₂ ( dondc) and M ₂ (dotpdc):

Here, metal M is Mg, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, dobpdc is 4,4'-dioxido-3,3'-biphenyldicarboxylate, and dobdc is is 2,5-dioxido-1,4-benzenedicarboxylate, o -dobdc is 4,5-dioxido-1,2-benzenedicarboxylate, m-dobdc is 4,6-dicarboxylate oxido-1,3-benzenedicarboxylate, dondc is 1,5-dioxide-2,6-naphthalenedicarboxylate, dotpdc is 4,4'-dioxido-3,3'-triphenyldica It is a voxylate.

According to the present invention, the amine may be a compound represented by the following [Formula 1]:

[Formula 1]

In the above [Formula 1],

Wherein R ₁ to R ₈ are each independently hydrogen or (CH _p ) _x (CH _q ) _y (CH _r ) _z , wherein n is each independently an integer from 1 to 20, and p, q and r are each independently is an integer from 0 to 3, and x, y, and z are each independently an integer from 0 to 20.

According to the present invention, the amine may be selected from the following compounds:

.

.

According to the present invention, the amine is ethylenediamine, 1-methylethylenediamine, 1,1-dimethylethylenediamine, N-ethylethylenediamine, N-methyl-1,3-diaminopropane (N-methyl-1,3 -diaminopropane), 1,3-diaminopentane (1,3-diaminopentane), 1,2-diaminopropane, 2,2-dimethyl-1,3-diaminopropane or N,N-dimethyl-1,3 -It may be diaminopropane.

According to the present invention, the carbon dioxide adsorbent may be formed in the form of a film.

According to the present invention, the carbon dioxide adsorbent may be coated on a predetermined substrate.

In this case, the substrate may be a Ti mesh, a filter, or activated carbon.

According to the present invention, a hydrophobic polymer binder is introduced into the metal-organic framework functionalized with amine so that the hydrophobic polymer covers the surface of the metal-organic framework, thereby blocking access of moisture, and consequently structurally It is possible to provide a carbon dioxide adsorbent capable of maintaining stability and exhibiting excellent adsorption performance.

1 shows the use of the polymer/amine-grafted metal-organic framework (epn-MOF@SBS) according to the present invention (composite membrane for adsorbing carbon dioxide, Ti mesh, filter for air purification, coating on activated carbon).
Figure 2 shows (a) optical image and (b) SEM image of epn-MOF80@SBS.
3 shows (a) PXRD measurement data and (b) IR spectrum data of epn-MOF and epn-MOF@SBS.
4 shows the results of measuring carbon dioxide adsorption performance of (a) epn-MOF, (b) epn-MOF60@SBS, (c) epn-MOF70@SBS, and (d) epn-MOF80@SBS.
5 shows the results of measuring water contact angles of (a) epn-MOF, (b) epn-MOF60@SBS, and (c) epn-MOF80@SBS.
6 shows the results of measuring carbon dioxide adsorption performance according to the exposure time of epn-MOF and epn-MOF80@SBS at 60% RH.
7 shows the results of repeated measurements of carbon dioxide adsorption performance of (a) epn-MOF and (b) epn-MOF80@SBS inside the chamber.
8 shows (a) Ti mesh, (b) optical images of Ti mesh@epn-MOF80@SBS, and (c) elemental mapping results of Ti mesh@epn-MOF80@SBS.
9 shows SEM images of (a) a Ti network and (b) a Ti mesh@epn-MOF80@SBS.
10 shows the results of repeated measurements of carbon dioxide adsorption performance of (a) Ti mesh and (b) Ti mesh@epn-MOF80@SBS inside the chamber.
11 shows (a) HEPA filter before epn-MOF80@SBS coating, (b) HEPA filter after epn-MOF80@SBS coating, (c) activated carbon before epn-MOF80@SBS coating, (d) epn-MOF80@SBS coating It shows an optical image of the activated carbon after
12 shows the results of repeated measurements of carbon dioxide adsorption performance of (a) Filter@epn-MOF80@SBS and (b) AC@epn-MOF80@SBS inside the chamber.
13 shows the results of measuring the water contact angle according to the mixing ratio of SBS and PDMS introduced into the MOF (1:1 for A, 1:2 for B, and 1:3 for C).
14 shows the result of measuring the carbon dioxide adsorption performance according to the mixing ratio of SBS and PDMS introduced into the MOF (1:1 for A, 1:2 for B, and 1:3 for C).
Figure 15 shows the mixing ratio of SBS and PDMS ((a) 1:1, (b) 1:2, (c) 1:3) introduced into the MOF after exposure for one day under 95% RH conditions. It shows the result of measuring carbon dioxide adsorption performance.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is one well known and commonly used in the art.

In the present invention, when the conventional MOF is exposed to a humid environment in which a large amount of moisture exists, such as an indoor environment with high relative humidity (eg, about 60% RH or more) or water vapor that accounts for about 5 to 7% of exhaust gas, It was devised to solve the problem that the carbon dioxide adsorption capacity may decrease due to the collapse of the structure or the deterioration of the bond with the amine group, and the present invention aims to provide a carbon dioxide adsorbent capable of maintaining structural stability from moisture.

To this end, the present invention provides a metal-organic skeleton in which amine is introduced at an open metal site; and a hydrophobic polymer binder coated on the surface of the metal-organic framework.

The introduction of the hydrophobic polymer binder covers the surface of the metal-organic framework and blocks access of moisture, thereby improving structural stability from moisture. The hydrophobic polymer binder is polystyrene (PS), acrylonitrile-butadiene It may be at least one styrene-based resin selected from the group consisting of styrene (ABS), styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS) and styrene-butadiene-rubber (SBR), , preferably SBS.

In addition, the present invention can enhance the water stability of the metal-organic framework through the introduction of a styrene-based resin as a hydrophobic polymer binder to maintain excellent carbon dioxide adsorption capacity. As can be seen from the results of the following examples, the metal - The weight ratio of the organic framework and the styrene-based resin is preferably 6:4 to 8:2, more preferably 7:3 to 8:2.

In addition, in order to further improve water stability, the hydrophobic polymer binder is selected from the group consisting of polydimethylsiloxane (PDMS), polytetrafluoroethylene PTFE, and polyvinylidene fluoride (PVDF) It may further include one or more hydrophobic polymer materials that are, and preferably may further include PDMS.

In addition, the present invention further enhances the water stability of the metal-organic framework by further including the hydrophobic polymer material in the hydrophobic polymer binder to maintain excellent carbon dioxide adsorption capacity, as can be seen from the results of the following examples. , It is preferable that the weight ratio of the styrene-based resin and the hydrophobic polymer material is 1:1 to 1:3.

The metal-organic framework according to the present invention may include M ₂ (dobpdc), M ₂ (dobdc), M ₂ ( o -dobdc), M ₂ ( m -dobdc), and M ₂ (dondc). ) and M ₂ (dotpdc). In this case, the metal M is Mg, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, dobpdc is 4,4'-dioxido-3,3'-biphenyldicarboxylate, dobdc is 2,5-dioxido-1,4-benzenedicarboxylate, o -dobdc is 4,5-dioxido-1,2-benzenedicarboxylate, m-dobdc is 4,6- Dioxido-1,3-benzenedicarboxylate, dondc is 1,5-dioxide-2,6-naphthalenedicarboxylate, dotpdc is 4,4'-dioxido-3,3'-triphenyl As a dicarboxylate, it can be represented by the following [General Formula 1].

[Formula 1]

In addition, the amine introduced into the metal-organic framework of the present invention may be a polyvalent amine containing at least one of primary to tertiary amine groups, and carbon dioxide is effectively captured through amine functionalization of the metal-organic framework. can do. In particular, for capturing carbon dioxide in the air, it is preferable to use a porous metal-organic skeleton in which high-density amine groups are introduced into the cavities. Adsorption enthalpy due to an interaction between an amine group and a carbon atom of CO ₂ can be remarkably improved through the introduction of the high-density amine group. Such amine functionalization is achieved by grafting an amine group to an open metal site of the metal-organic framework, and the open metal site acts as a Lewis acid. In this case, the primary amine group can be well coordinated to the open metal site by including two hydrogen groups. In addition, the remaining free amine groups can effectively trap CO ₂ entering the cavity.

Specifically, the amine may be a compound represented by the following [Formula 1]:

[Formula 1]

In the above [Formula 1],

Wherein R ₁ to R ₈ are each independently hydrogen or (CH _p ) _x (CH _q ) _y (CH _r ) _z , wherein n is each independently an integer from 1 to 20, and p, q and r are each independently is an integer from 0 to 3, and x, y, and z are each independently an integer from 0 to 20.

In addition, the amine may be selected from the following compounds:

.

.

In addition, the amine is ethylenediamine, 1-methylethylenediamine, 1,1-dimethylethylenediamine, N-ethylethylenediamine, N-methyl-1,3-diaminopropane (N-methyl-1,3-diaminopropane) , 1,3-diaminopentane, 1,2-diaminopropane, 2,2-dimethyl-1,3-diaminopropane or N,N-dimethyl-1,3-diamino It can be propane.

According to the present invention, the metal-organic framework coated with a hydrophobic polymeric binder on the surface and introduced with amine is a carbon dioxide adsorbent for air purification in the form of a composite membrane for carbon dioxide adsorption, a Ti mesh, a filter for air purification, or a coating on activated carbon. can be used

Specifically, the carbon dioxide adsorbent according to the present invention may be formed in the form of a film. In addition, the carbon dioxide adsorbent may be coated on a substrate and used. In this case, the substrate may be a Ti mesh, filter, or active carbon (AC).

In the present invention, through the following examples, it is shown that the carbon dioxide adsorbent according to the present invention can effectively capture carbon dioxide at 400-5000 ppm applicable to an environment where a large amount of moisture exists (40-100% RH conditions) and air purification. As confirmed, it was confirmed that according to the present invention, a carbon dioxide adsorbent capable of exhibiting excellent adsorption performance by maintaining structural stability from moisture can be provided.

[Example]

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Example . polymer/ Amine Grafted Metal- organic skeleton Preparation of based carbon dioxide adsorbent

epn - Mg ₂ ( dobpdc ) (below ' epn -MOF') synthesis

First, 7.84 mg of H ₄ dobpdc was dissolved in 75 mL of DMF, and 11.63 mg of MgBr ₂ H ₂ O was dissolved in 75 mL of EtOH, followed by reaction at 130 °C for 72 hours using a 300 mL high-pressure reactor to synthesize Mg ₂ (dobpdc). In order to remove the DMF coordinated to the open metal site of synthesized Mg ₂ (dobpdc), it was supported in MeOH for 3 days, and 112.2 mL of 1,3-diaminopentane (epn) was dissolved in 140 mL of hexane, and 2 g of Mg ₂ (dobpdc) was dissolved. After adding, the reaction was performed at 50° C. for 12 hours under ultrasound to obtain epn-functionalized epn-MOF.

X% epn - Mg ₂ ( dobpdc )@SBS (hereafter 'epn-MOFX@SBS') (X = epn - Mg ₂ (dobpdc) 60, 70, 80 weight content) manufacturing composite membranes

Polystyrene-block-polybutadiene-block-polystyrene (hereafter SBS) polymer (200 mg at X = 60, 100 mg at X = 70, 100 mg at X = 80) was added to 4 mL of toluene, stirred for 6 hours to dissolve, and then epn -Add MOF (300 mg at X = 60, 350 mg at X = 70, 400 mg at X = 80) and epn (0.11 mL at X = 60, 0.13 mL at X = 70, 0.15 mL at X = 80) The mixture was stirred and dispersed for 24 hours to prepare a mixed solution of epn-MOFX@SBS. Thereafter, the mixed solution was cast on a Teflon plate using a doctor blade (height: 100 μm) and dried in an oven at 70° C. for 15 minutes to prepare a composite membrane.

Ti fabrication of mesh@epn-MOF80@SBS

The mixed solution (epn-MOF80@SBS) prepared in the same way as described above was sprayed on the Ti net using a spray gun, and then the coated Ti net was dried in an oven at 70°C for 15 minutes. was repeated 5 times to prepare Ti mesh@epn-MOF80@SBS.

Manufacturing Filter@epn-MOF80@SBS

The mixed solution (epn-MOF80@SBS) prepared in the same manner as described above was sprayed on the HEPA filter using a spray gun, and then the coated HEPA filter was dried in an oven at 70 ° C for 15 minutes. was repeated 5 times to prepare Filter@epn-MOF80@SBS.

Manufactured by AC@epn-MOF80@SBS

The mixed solution (epn-MOF80@SBS) prepared in the same way as described above was sprayed on activated carbon using a spray gun, and then the coated activated carbon was dried in an oven at 70 ° C for 15 minutes. AC@epn-MOF80@SBS was prepared by repeating several times.

Manufacture of epn-MOF70@PDMS@SBS-X (X = A, B, C)

A metal-organic framework (epn-MOF70@PDMS@SBS-X) (X = A, B, C) in which PDMS was further introduced into the hydrophobic polymer binder was prepared as follows (A is a mixture of SBS and PDMS) The ratio is 1:1, B is 1:2, and C is 1:3). First, polydimethylsiloxane (PDMS) prepolymer (Sylgard 184 A) (A = 75 g, B = 100 g, C = 112.5 g) and SBS (A = 75 g, B = 50 g, C = 37.5 g) were added to 4 mL of toluene. and dissolved by stirring for 6 hours. Thereafter, 350 mg of epn-MOF and a curing agent (Sylgard 184B) (PDMS to curing agent ratio = 10:1) were added and dispersed by stirring for 24 hours. After the dispersion was completed, the solution was poured into a rubber mold and dried while blowing nitrogen gas at room temperature to prepare epn-MOF70@PDMS@SBS-X (X = A, B, C).

Experimental example 1. According to the introduction of SBS polymer of composite membrane Analysis of basic characteristics and adsorption/desorption behavior

The basic characteristics of the prepared composite membrane were analyzed.

First, (a) an optical image and (b) an SEM image of the composite film including epn-MOF80@SBS were measured, and the results are shown in FIG. 2 below. Through this, it was confirmed that the prepared composite membrane had a flexible property (FIG. 2a), the thickness was about 55 μm, and it was confirmed that epn-MOF particles were evenly dispersed therein (FIG. 2b).

Next, (a) PXRD measurement data and (b) IR spectrum data of the composite film including epn-MOF and epn-MOF@SBS were measured, and the results are shown in FIG. 3 below. First, through X-ray diffraction analysis, it was confirmed that the crystallinity of the SBS polymer was maintained even after the introduction of the SBS polymer into the epn-MOF (Fig. 3a). By confirming that the ,4-bond peak appears at 965 cm ^{-1 ,} it was confirmed that the SBS polymer was well introduced (FIG. 3b).

Next, in order to confirm the carbon dioxide adsorption performance of the composite membranes including the manufactured epn-MOF60@SBS, epn-MOF70@SBS, and epn-MOF80@SBS, the adsorption/desorption behavior was analyzed using a thermogravimetric analyzer. The results are shown in Figure 4 below. At this time, each composite membrane was adsorbed at 30 °C and desorbed at 70 °C under a condition of 1000 ppm carbon dioxide partial pressure. As a result of the analysis, it was confirmed that epn-MOF exhibited adsorption performance of 13 wt%, epn-MOF60@SBS 5.07 wt%, epn-MOF70@SBS 7.01 wt%, and epn-MOF80@SBS 7.88 wt%.

Experimental example 2. Following the introduction of SBS polymer of composite membrane Hydrophobicity effect and water stability analysis

In order to confirm the effect of increasing hydrophobicity before and after introducing the SBS polymer, the water contact angles of the composite membranes including epn-MOF and epn-MOF@SBS were measured, and the results are shown in FIG. 5 below. As a result of the measurement, it was confirmed that the contact angle of the hydrophilic epn-MOF was 0°, and it showed a hydrophobic property according to the introduction of the SBS polymer, and the contact angle increased as the SBS content increased, showing a tendency to increase hydrophobicity.

Next, in order to check the water stability of the composite membrane, epn-MOF and epn-MOF80@SBS were exposed for 30 days at 30 ° C and 60% RH, and then the carbon dioxide adsorption performance was measured using a thermogravimetric analyzer, and the results were It is shown in Figure 6 below. As a result of the measurement, the initial carbon dioxide adsorption capacity of epn-MOF was 13 wt%, but after exposure to 60% RH for 30 days, the adsorption capacity rapidly decreased to 4.9 wt%, whereas the initial carbon dioxide adsorption capacity of epn-MOF80@SBS was showed 8.03 wt% and showed an adsorption performance of 7.99 wt% even after exposure to 60% RH for 30 days. Through this, it was confirmed that the moisture stability of the carbon dioxide adsorbent is greatly improved when the hydrophobic polymer is introduced according to the present invention. .

Experimental example 3. Following the introduction of SBS polymer of composite membrane Practical usability evaluation

In order to evaluate the possibility of repeatedly using epn-MOF80@SBS indoors, the carbon dioxide adsorption performance was repeatedly measured by forming conditions similar to the indoor environment in a sealed chamber, and the results are shown in FIG. 7 below. . 7 shows the results of repeated measurements of carbon dioxide adsorption performance of (a) epn-MOF and (b) epn-MOF80@SBS inside the chamber. The inside of the chamber was conducted in a carbon dioxide environment at 30° C., 60% RH, and 1000 ppm concentration. Adsorption was carried out for 3 hours under the above chamber internal conditions, and carbon dioxide adsorption performance was repeatedly measured 10 times by desorption at 130 ° C for 2 hours. As a result of the measurement, the epn-MOF showed a continuous decrease in carbon dioxide adsorption performance as the experiment was repeated (first: 731ppm adsorption, tenth: 211ppm adsorption), while epn-MOF80@SBS showed a decrease in carbon dioxide adsorption performance for 10 times. Even after repeated measurements, it was found that the initial performance was continuously maintained (first: 455ppm adsorption, tenth: 447ppm adsorption), and through this, when the hydrophobic polymer was introduced according to the present invention, the water stability of the carbon dioxide adsorbent was greatly improved, It was confirmed that the carbon dioxide adsorption performance could be maintained even when reused.

Experimental example 4. Ti Analysis of basic characteristics and carbon dioxide adsorption performance of mesh@epn-MOF80@SBS

Optical images of the Ti mesh and Ti mesh@epn-MOF80@SBS and elemental mapping analysis of the Ti mesh@epn-MOF80@SBS were performed, and the results are shown in FIG. 8 below. First, through the optical image of Ti mesh@epn-MOF80@SBS, the Ti mesh before epn-MOF80@SBS coating was gray, but after coating it turned to light purple, confirming that epn-MOF80@SBS was well coated (Fig. 8a, b). In addition, through the elemental mapping results, it was confirmed that Mg, one of the elements constituting the epn-MOF, was evenly spread, and through this, it was confirmed that the epn-MOF80@SBS was evenly coated on the surface of the Ti mesh (FIG. 8c).

Next, SEM image analysis of (a) Ti mesh and (b) Ti mesh@epn-MOF80@SBS was performed, and the results are shown in FIG. 9 below. 9, it was confirmed that the Ti mesh before coating had a smooth surface, while the surface of Ti mesh@epn-MOF80@SBS after coating was roughened by epn-MOF80@SBS.

Next, in order to evaluate the feasibility of the Ti mesh@epn-MOF80@SBS in an actual indoor environment, carbon dioxide adsorption performance was repeatedly measured in a closed chamber, and the results are shown in FIG. 10 below. 10 shows the results of repeated measurements of carbon dioxide adsorption performance of (a) Ti mesh and (b) Ti mesh@epn-MOF80@SBS inside the chamber. The inside of the chamber was conducted in a carbon dioxide environment at 30° C., 60% RH, and 1000 ppm concentration. Adsorption was performed for 3 hours under the above chamber internal conditions, and desorption was performed at 100 ° C. for 2 hours, and the carbon dioxide adsorption performance was repeatedly measured 10 times. As a result of the measurement, the performance of the Ti mesh continued to decrease while the experiment was repeated 10 times (1st adsorption: 851ppm, 10th adsorption: 52ppm), while Ti mesh@epn-MOF80@SBS adsorbed carbon dioxide 10 times. It was found that the performance was continuously maintained even during repeated performance measurements (first: 586ppm adsorption, tenth: 582ppm adsorption), and through this, the water stability of the carbon dioxide adsorbent was greatly improved when the hydrophobic polymer was introduced according to the present invention. It was confirmed that the carbon dioxide adsorption performance could be maintained even when reused.

Experimental example 5. epn-MOF80@SBS coated with HEPA filter Carbon dioxide adsorption performance evaluation of activated carbon

Filter@epn-MOF80@SBS and AC@epn-MOF80@SBS were prepared by spraying the mixed solution (epn-MOF80@SBS) prepared according to the above example to the HEPA filter and activated carbon using a spray gun (Fig. 11).

Next, in order to evaluate the possibility of using Filter@epn-MOF80@SBS and AC@epn-MOF80@SBS in an actual indoor environment, carbon dioxide adsorption performance was repeatedly measured in a closed chamber, and the results are shown in FIG. 12 . 12 shows the results of repeated measurements of carbon dioxide adsorption performance of (a) Filter@epn-MOF80@SBS and (b) AC@epn-MOF80@SBS inside the chamber. The inside of the chamber was conducted in a carbon dioxide environment at 30° C., 60% RH, and 1000 ppm concentration. Adsorption was performed for 3 hours under the above chamber internal conditions, desorption was performed at 100 ° C. for 2 hours, and carbon dioxide adsorption performance was repeatedly measured 10 times. As a result of the measurement, it was found that both Filter@epn-MOF80@SBS and AC@epn-MOF80@SBS continuously maintained their performance even during the repeated measurement of carbon dioxide adsorption performance 10 times. When introduced, it was confirmed that the moisture stability of the carbon dioxide adsorbent was greatly improved, and the carbon dioxide adsorption performance could be maintained even when reused.

Experimental example 6. PDMS Evaluation of hydrophobic effect, carbon dioxide adsorption performance and moisture stability according to additional introduction

In order to confirm the effect of increasing hydrophobicity according to the addition of PDMS polymer, the water contact angle of epn-MOF70@PDMS@SBS-X (X = A, B, C) (the ratio of MOF is fixed at 71.4%) was measured, and the result was It is shown in Figure 13 below. As a result of the measurement, it was confirmed that as the content of PDMS introduced increases, the contact angle increases and thus the hydrophobicity tends to increase.

Next, the carbon dioxide adsorption performance according to the mixing ratio of SBS and PDMS introduced into the MOF (A is 1:1, B is 1:2, and C is 1:3) was measured through thermogravimetric analysis, and the results are shown below. 14. Thermogravimetric analysis was conducted in an environment with a carbon dioxide concentration of 1000 ppm, adsorption at 30 °C for 6 hours, and desorption at 70 °C for 30 minutes. As a result of the measurement, it was confirmed that the carbon dioxide adsorption performance of A, B, and C was 10.63 wt%, 13.12 wt%, and 11.61 wt%, respectively.

Next, for water stability evaluation, after exposure for one day under 95% RH conditions, the mixing ratio of SBS and PDMS introduced into the MOF ((a) is 1:1, (b) is 1:2, (c) is Carbon dioxide adsorption performance was measured according to 1:3), and the results are shown in FIG. 15 below. As a result of the measurement, when the mixing ratio of SBS and PDMS was 1:1, the carbon dioxide adsorption performance decreased from 10.63 wt% to 9.1 wt% after exposure, and when the mixing ratio of SBS and PDMS was 1:2, the carbon dioxide adsorption performance decreased to 13.12 It decreased from wt% to 8.04 wt%, and when the mixing ratio of SBS and PDMS was 1:3, the carbon dioxide adsorption performance decreased from 11.61 wt% to 11.13 wt%. Through this, it was confirmed that the moisture stability was further improved when PDMS was additionally introduced, and in particular, when the mixing ratio of SBS and PDMS was 1:3, it was confirmed that the highest moisture stability was exhibited.

Having described specific parts of the present invention in detail above, it is clear that these specific descriptions are only preferred embodiments for those skilled in the art, and the scope of the present invention is not limited thereby. something to do. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

metal-organic skeletons in which amines are introduced at open metal sites; and
A carbon dioxide adsorbent comprising a hydrophobic polymer binder coated on the surface of the metal-organic framework. According to claim 1,
The hydrophobic polymer binder is polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), styrene-ethylene-butylene-styrene (SEBS), styrene-butadiene-styrene (SBS) and styrene-butadiene-rubber (SBR). ) Carbon dioxide adsorbent, characterized in that at least one styrene-based resin selected from the group consisting of. According to claim 2,
The carbon dioxide adsorbent, characterized in that the weight ratio of the metal-organic framework and the styrenic resin is 6:4 to 8:2. According to claim 2,
The hydrophobic polymer binder further includes at least one hydrophobic polymer material selected from the group consisting of polydimethylsiloxane (PDMS), polytetrafluoroethylene PTFE, and polyvinylidene fluoride (PVDF) Carbon dioxide adsorbent, characterized in that to do. According to claim 4,
The carbon dioxide adsorbent, characterized in that the weight ratio of the styrene-based resin and the hydrophobic polymer material is 1: 1 to 1: 3. According to claim 1,
The metal organic framework may include M ₂ (dobpdc), M ₂ (dobdc), M ₂ ( o -dobdc), M ₂ ( m -dobdc), M ₂ (dondc) and M ₂ A carbon dioxide adsorbent, characterized in that selected from the group consisting of (dotpdc):
Here, metal M is Mg, Ti, V, Cr, Mn, Fe, Co, Ni, Cu or Zn, dobpdc is 4,4'-dioxido-3,3'-biphenyldicarboxylate, and dobdc is is 2,5-dioxido-1,4-benzenedicarboxylate, o -dobdc is 4,5-dioxido-1,2-benzenedicarboxylate, m-dobdc is 4,6-dicarboxylate oxido-1,3-benzenedicarboxylate, dondc is 1,5-dioxide-2,6-naphthalenedicarboxylate, dotpdc is 4,4'-dioxido-3,3'-triphenyldica It is a voxylate. According to claim 1,
The carbon dioxide adsorbent, characterized in that the amine is a compound represented by the following [Formula 1]:
[Formula 1]

In the above [Formula 1],
Wherein R ₁ to R ₈ are each independently hydrogen or (CH _p ) _x (CH _q ) _y (CH _r ) _z , wherein n is each independently an integer from 1 to 20, and p, q and r are each independently is an integer from 0 to 3, and x, y, and z are each independently an integer from 0 to 20. According to claim 1,
A method for producing a carbon dioxide adsorbent, characterized in that the amine is selected from the following compounds:

. According to claim 1,
The amine is ethylenediamine, 1-methylethylenediamine, 1,1-dimethylethylenediamine, N-ethylethylenediamine, N-methyl-1,3-diaminopropane, 1 ,3-diaminopentane (1,3-diaminopentane), 1,2-diaminopropane, 2,2-dimethyl-1,3-diaminopropane or N,N-dimethyl-1,3-diaminopropane Carbon dioxide adsorbent, characterized in that. According to claim 1,
The carbon dioxide adsorbent is characterized in that the carbon dioxide adsorbent is formed in the form of a film. According to claim 1,
The carbon dioxide adsorbent is characterized in that the carbon dioxide adsorbent is coated on a predetermined substrate. According to claim 11,
The carbon dioxide adsorbent, characterized in that the substrate is a Ti mesh, a filter or activated carbon.

Images