KR102278739B1 - Absorbent comprising zeolitic imidazolate framework for absorbing chemical warfare agents and application thereof - Google Patents

Abstract

The present invention relates to a chemical agent adsorbent using ZIF and its utilization, and more specifically, ZIF (Zeolitic imidazolate framework)-8, ZIF-67 or both, and the adsorption function of chemical agent molecules in a moisture environment ZIF-based composites and articles comprising: a chemical agent adsorbent; and a chemical agent adsorbent. Furthermore, the present invention relates to a method for producing a ZIF-based composite according to the present invention.

Description

Chemical agent adsorbent using ZIF and its application {ABSORBENT COMPRISING ZEOLITIC IMIDAZOLATE FRAMEWORK FOR ABSORBING CHEMICAL WARFARE AGENTS AND APPLICATION THEREOF}

The present invention relates to a chemical agent adsorbent using ZIF and its utilization.

Blister agents (eg, mustard gas, bis-(2-chloroethyl)sulfide, HD) are chemical warfare agents that act on the skin to form blisters and have properties for the digestive, ocular and respiratory systems. HD mainly damages organs in immediate contact with the liquid or vapor phase of HD, and HD has relatively nonselective electrophilic centers. In fact, in the battlefield, it is used for the purpose of contamination to weaken the combat power by inflicting fatal wounds on the allies and limit the use of enemy supplies or facilities.

Until now, various studies have been conducted to develop effective detoxifying catalysts for HD, but currently reported catalysts or chemical detoxifying products for HD are not completely safe for humans. Therefore, in order to remove the contamination of HD, it is necessary to develop a fast adsorbent that does not cause additional safety problems to people or the environment.

Recently, blister agent gas molecular adsorbents based on high surface materials such as activated carbon, metal oxide nanoparticles, zeolites and MOFs have been reported, and activated carbon based materials are predominant. However, in the case of the activated carbon adsorbent used, the performance varies depending on the environment. In particular, the adsorption capacity is lowered in a high humidity environment, and it is difficult to safely and quickly respond when exposed to a blister agent in a high humidity environment or aqueous solution. Activated carbon is structurally a two-dimensional structure rather than a porous structure. That is, the adsorbed molecule is exposed to the environment, and an additional chemical reaction may occur with an externally active molecule. As a result, secondary by-products are created, and harmful by-products themselves are exposed to the human body as they are. In other words, despite having low solubility in water, the blistering agent molecules cause a hydration reaction with moisture in a significant amount, generating secondary harmful substances such as hydrochloric acid. Therefore, there is an urgent need for a material capable of rapidly and safely capturing and desorbing adsorbed molecules in a safe place without additional chemical reaction.

In order to solve the above-mentioned problems, the present invention uses ZIF to rapidly adsorb chemical agent molecules in a moisture environment, stably capture chemical agent molecules in nanopores without additional chemical reaction, and rapidly in a specific environment. To provide a chemical agent adsorbent capable of desorption.

In the present invention, the synthesis and growth of ZIF is performed on a substrate, and the chemical agent molecules are rapidly adsorbed in a moisture environment using ZIF, and the chemical agent molecules are stably captured in nanopores without additional chemical reaction, and specific To provide a ZIF-based composite capable of rapid desorption from the environment.

The present invention provides an article comprising a chemical agent adsorbent or a ZIF-based complex according to the invention and having a chemical agent adsorption function, which is used to treat and/or eliminate as well as a protective and/or protective function from chemical agents will do

The present invention provides a method for producing a ZIF-based composite according to the present invention.

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

According to an embodiment of the present invention, it relates to a chemical agent adsorbent comprising zeolitic imidazolate framework (ZIF)-8, ZIF-67 or both, and having an adsorption function of chemical agent molecules in a moisture environment.

According to an embodiment of the present invention, the chemical agent may be a blister agent.

According to an embodiment of the present invention, the moisture environment, 50% or more; 70% or more; Or it may be an atmospheric environment having a humidity of 80% or more.

According to an embodiment of the present invention, the moisture environment, in the aqueous solution or in a wet state in the aqueous solution, the aqueous solution, 50% or more; 70% or more; Or it may contain 80% or more of water.

According to an embodiment of the present invention, the chemical agent adsorbent may be regenerated by desorption of the adsorbed chemical agent by washing with a solvent having chemical agent solubility.

According to one embodiment of the present invention, a substrate; and ZIF-8, ZIF-67, or both coated on the substrate, wherein the ZIF-based composite has a function of adsorbing chemical agent molecules in a moisture environment.

According to an embodiment of the present invention, the ZIF-8, ZIF-67 or both are synthesized and coated on the substrate, and the ZIF-8, ZIF-67 or both may be nanocrystals. .

According to an embodiment of the present invention, the ZIF-8, ZIF-67 or both may be included in an amount of 0.01 wt% to 30 wt% of the substrate.

According to an embodiment of the present invention, the substrate may include fibers, fabrics, or both, and the substrate may be surface-treated with a silylating agent.

According to one embodiment of the present invention, there is provided an article comprising a chemical agent adsorbent according to the present invention or a ZIF-based complex according to the present invention, and having a chemical agent molecular adsorption function.

According to an embodiment of the present invention, the article may be a protective garment, a gas mask, a mask, a filter, a glove, a garment, a sheet, a film or a mat.

According to an embodiment of the present invention, the method comprising: preparing a substrate; Plasma surface treatment on the substrate; treating a silylating agent on the plasma surface-treated substrate; contacting the substrate treated with the silylating agent with a metal salt solution; and contacting the substrate with an imidazole compound solution to synthesize and grow ZIF; It relates to a method for preparing a ZIF-based complex for adsorption of chemical agents, comprising:

According to an embodiment of the present invention, the ZIF may be ZIF-8 or ZIF-67.

According to an embodiment of the present invention, the substrate may include fibers, fabrics, or both.

According to an embodiment of the present invention, the fiber is, pulp, hemp fiber, cotton, hemp, wool, silk, cellulose, polyamide (polyamide), acrylic (acrylic), vinyl nylon (vinyl-nylon), polyester, It may include at least one selected from the group consisting of polyimide, aramid, polyethylene, polyethylene terephthalate, polylactic accid, and nylon.

According to an embodiment of the present invention, the silylating agent is the aminosilane compound,

The aminosilane compound is N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl) -3-Aminopropyl triethoxysilane, (3-aminopropyl) trimethoxysilane ((3-Aminopropyl) trimethoxysilane; APS), (3-aminopropyl) triethoxysilane ((3-Aminopropyl) triethoxysilane) and It may include at least one selected from the group consisting of N-(3-aminopropyl)-dimethyl-ethoxysilane.

According to an embodiment of the present invention, the metal salt solution may include a metal salt and an alcohol solvent.

According to an embodiment of the present invention, the imidazole compound is 2-ethylimidazole, 2-decylimidazole, 2-hextylimidazole, 2-isopropylimidazole, and 2-undecylimida. Sol, 2-heptanedecylimidazole, 1,4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2- Methyl imidazole, 1-benzyl-2-phenyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2- It may include at least one selected from the group consisting of undecyl imidazole and 1-cyanoethyl-2-phenyl imidazole.

The present invention applies ZIF-8 and ZIF-67 to have ultra-fast adsorption rate, large adsorption capacity, excellent chemical and solvent stability, and excellent reusability, and to remove chemical agents, such as blistering agents, from environmental water. and/or processable chemical agent adsorbents.

The present invention provides a ZIF-based composite capable of removing and/or treating a chemical agent, for example a blister agent, in environmental water by easily growing the chemical agent adsorbent according to the invention on a substrate, It is possible to provide a composite excellent in reusability by adsorption and desorption of an agent and various functional articles using the same.

1 exemplarily illustrates a process for removing a chemical agent by a chemical agent adsorbent according to the present invention, according to an embodiment of the present invention.
FIG. 2 shows (a) XRD patterns, (b) SEM images, and (c) BET surface areas of ZIF-8 and ZIF-67 prepared in Examples of the present invention according to an embodiment of the present invention.
Figure 3 shows the total removal rate (solid dots), hydrolysis and adsorption of CEES in the presence of ZIF-8 (a) and ZIF-67 (b) prepared in the example of the present invention, according to an embodiment of the present invention; indicates selectivity.
Figure 4 shows the total removal rate of CEES in the presence of ZIF-8 and ZIF-67 prepared in Examples of the present invention, according to an embodiment of the present invention, for 5 minutes at 25 ℃ water / ethanol (1 mL, 9:1, v/v) according to (a) reaction time and (b) temperature are shown.
FIG. 5 shows adsorption isotherms and model fitting results of (a) ZIF-8 and (b) ZIF-67 prepared in Examples of the present invention according to an embodiment of the present invention.
6 shows the reusability of ZIF-8 and ZIF-67 for CEES adsorption prepared in the example of the present invention, according to an embodiment of the present invention.
7 shows the removal rate, hydrolysis and adsorption amount of CEES for ZIF-8 and ZIF-67 and various adsorbents prepared in Examples of the present invention, according to an embodiment of the present invention.
8 shows the total removal rate for actual HD according to the reaction time in the presence of ZIF-8 and ZIF-67 prepared in the example of the present invention according to an embodiment of the present invention.
Figure 9, according to an embodiment of the present invention, shows an exemplary process of the manufacturing method of ZIF-8 and ZIF-67 / cotton composite according to the present invention.
10 shows (a) images, (b) SEM images, and (c) of ZIF-8 and ZIF-67 grown on cotton prepared in Examples of the present invention, and pure cotton according to an embodiment of the present invention; ) shows the XRD pattern.
11 is, according to an embodiment of the present invention, (a) the adsorption test process of CEES using the ZIF-8-coated side and the ZIF-67-coated side prepared in the Example of the present invention, and (b) The content of CEES extracted from each cotton sample and remaining on the glass is shown.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms used in this specification are terms used to properly express the preferred embodiment of the present invention, which may vary according to the intention of the user or operator or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification. Like reference numerals in each figure indicate like elements.

Throughout the specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components.

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

The present invention relates to a chemical agent adsorbent, and according to an embodiment of the present invention, the chemical agent adsorbent includes a Zeolitic imidazolate framework (ZIF), and is a chemical agent molecule in various environments, for example, a moisture environment. It can exhibit fast adsorption kinetics, good solvent stability, high adsorption capacity, and regenerating capacity.

According to an embodiment of the present invention, the chemical agent adsorbent may include ZIF-8, ZIF-67, or both. The ZIF-8 and ZIF-67 are porous materials having a structure similar to that of zeolite, for example, M (2-methylimidazole) ₂ (M = Co or Zn) Sodalite (SOD, sodalite) structure having a chemical formula can be ZIF-8 and ZIF-67 have strong hydrophobic properties inside the inner nanopores, and in the case of molecules trapped inside, they limit contact with other active molecules outside, making it possible to stably capture chemical agent molecules. It is a nanoporous body. For example, ZIF-8 and ZIF-67 rapidly adsorb chemical agent molecules within seconds under moisture environment, and after adsorption, chemical agent molecules are perfectly embedded in the nanopores. In addition, up to 100% of the adsorbed chemical agent molecules can be desorbed by a specific environment, a desorption process, and the like.

The moisture environment is an environment containing an aqueous medium, 50% or more; 70% or more; Or it may be an atmospheric environment having a humidity of 80% or more. The humidity may be relative humidity. In addition, the moisture environment is a chemical agent, an adsorbent, or both in an aqueous solution or in a wet state. The aqueous solution is 50% or more; 70% or more; 80% or more; or 90% or more of water. For example, the aqueous solution may be a mixture of water and an alcohol solvent, and a mixing ratio of water and alcohol may be 50:50 to 99:1 (v/v). For example, the alcohol may include methanol, ethanol, or both, and the polarity of the aqueous solution may be adjusted by mixing water and an alcohol solvent to improve the adsorption performance of the chemical agent.

The process of removing or treating a chemical agent using a general catalyst is mainly made of the hydrolysis function, but the present invention relates to the chemical agent by application of ZIF-8 and ZIF-67, moisture environment, or control of the polarity of the aqueous solution. By lowering the rate of hydrolysis during removal or treatment, the generation of contaminants can be reduced, and rapid adsorption can be achieved.

Referring to FIG. 1, FIG. 1 exemplarily illustrates a process for removing a chemical agent by a chemical agent adsorbent according to the present invention, according to an embodiment of the present invention. That is, the hydrolysis and adsorption processes of the chemical agents of ZIF-8 and ZIF-67, for example, chemical agent simulated CEES are exemplarily shown. In Fig. 1, since the internal pores of ZIF-8 and ZIF-67 exhibit strong hydrophobicity, hydrophobic CEES molecules are selectively adsorbed inside the pores in a polar medium such as water/ethanol aqueous solution, and the rest in water/ethanol aqueous solution. CEES is hydrolyzed. CEES molecules are hydrolyzed into ethyl 2-hydroxyethyl sulfide (EHES) and ethoxyethyl sulfide (EOES) while releasing HCl in aqueous solution, but ZIF-8 and ZIF-67 according to the present invention rapidly adsorb CEES molecules to hydrolyze them. Since it can reduce toxic pollutants by hydrolysis, it is possible to stably remove or treat CEES molecules.

for example, at least 50% of the total removal of chemical agents by the chemical agent adsorbent; 60% or more; 80% or more; Alternatively, 90% or more may be due to the adsorption function.

The chemical agent is a blistering agent, for example, HD (Distilled Mustard, bis- (2-chloroethyl) sulfide), HN-1 (Nitrogen Mustard, bis- (2-chloroethyl) ethylamine), HN-2 (bis- (2-chloroethyl) methylamine) and L (Lewisite, Dichloro- (2-chlorovinyl) arsine)) or may include at least one selected from the group consisting of their simulators, but is not limited thereto.

The chemical agent adsorbent is regenerated by desorbing the adsorbed chemical agent molecules, and can be reused repeatedly. For example, the adsorbed chemical agent can be quickly and safely desorbed by washing with a solvent having solubility of the adsorbed chemical agent, and the adsorbent can be regenerated and reused. For example, the solvent is an organic solvent having solubility of the blistering agent, and may be acetonitrile.

The present invention relates to a ZIF-based complex comprising a chemical agent adsorbent according to the present invention. According to one embodiment of the present invention, the ZIF-based complex has fast adsorption kinetics and high adsorption capacity for chemical agents. , has good solvent stability and regenerating ability, rapidly adsorbs chemical agent molecules, especially in a moisture environment, and can treat or remove chemical agents without or with minimal additional chemical reaction. In addition, the chemical agent is safely desorbed by a specific environment and a desorption process, and the complex can be regenerated and reused. The moisture environment, the adsorption process, the desorption process, etc. are the same as those mentioned in the chemical agent adsorbent.

According to an embodiment of the present invention, the ZIF-based composite comprises: a substrate; ZIF-8, ZIF-67 or both coated on the substrate.

The substrate includes a fiber, a textile, or both, and the fiber is kraft pulp, hemp fiber, linen, cotton, dioscorea, etc. of plant fiber; animal fibers such as wool and silk; cellulose; And polyamide, acrylic (acrylic), vinyl nylon (vinyl-nylon), polyester, polyimide (polyimide), aramid (aramid), polyethylene (poly etylene), polyethylene terephthalate (polyethylene terephthalate), polylac It may include at least one selected from the group consisting of synthetic fibers such as polylactic accid and nylon, but is not limited thereto.

The substrate may be 1 μm or more, 1 μm to 10 mm, 1 μm to 5 mm; Alternatively, it may have a thickness of 100 μm to 1 mm, and the substrate may include a single or multiple layers, and in the case of multiple layers, the chemical agents of each layer may be the same or different.

The fabric may include at least one selected from the group consisting of a cotton fabric, a hemp fabric, a wool fabric, a silk fabric, a blend fabric, a cross fabric, a non-woven fabric, and a microfiber fabric, but is not limited thereto.

The ZIF-8, ZIF-67 or both are nanocrystals synthesized and grown according to the surface of the substrate, for example, 1 nm or more; more than 10 nm; greater than 100 nm; 200 nm or more; It may have a size of 500 nm or more.

The ZIF-8, ZIF-67 or both of the above base material is 0.001% by weight or more; 0.1% to 30% by weight; 0.1% to 10% by weight; Or 0.1 wt% to 1 wt% may be included. When it is included within the above content range, rapid adsorption to chemical agent molecules is achieved, the chemical agent is stably captured, and can be regenerated by a specific environment and desorption process.

The ZIF-based complex was directly synthesized and grown on the substrate by ZIF-8, ZIF-67, or both. Prior to the synthesis of ZIF-8 and ZIF-67, the substrate is surface treated with a silylating agent. The silylating agent is the aminosilane compound, for example, the aminosilane compound is N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3- Aminopropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, (3-aminopropyl)trimethoxysilane ((3-Aminopropyl)trimethoxysilane; APS), (3-amino It may include at least one selected from the group consisting of propyl) triethoxysilane ((3-Aminopropyl) triethoxysilane) and N-(3-aminopropyl)-dimethyl-ethoxysilane.

The present invention relates to an article comprising a chemical agent adsorbent according to the invention and a ZIF-based complex, said article comprising the treatment or removal of the chemical agent, protection or defense from the chemical agent, and/or the human body by the chemical agent It can be used to treat injuries. For example, the article has the function of adsorbing chemical agent molecules, rapidly adsorbing the chemical agent in a moisture environment, desorbing the adsorbed chemical agent by a specific environment, a desorption process, and can be reused. The moisture environment, the adsorption process, the desorption process, etc. are the same as those mentioned in the chemical agent adsorbent.

For example, the article is used for protection or defense against chemical agents and is a portable article, and more specifically, such as a protective mask, suit, glove, filter, respirator, hazmat suit, protective clothing, sheet, film and mat, etc. It is a protective equipment, and may further include a cigarette filter, a cleaning mat, clothing, and the like.

The present invention relates to a method for producing a ZIF-based composite according to the present invention, and according to an embodiment of the present invention, the method comprising: preparing a substrate; Plasma surface treatment on the substrate; treating a silylating agent on the plasma surface-treated substrate; contacting the substrate treated with the silylating agent with the metal salt solution; and contacting the substrate with the imidazole compound solution to synthesize and grow ZIF; may include.

According to an embodiment of the present invention, the step of preparing the substrate includes preparing a substrate including a fiber, a fabric, or both, and is the same as described in the ZIF-based composite.

In the plasma surface treatment on the substrate, the surface may be modified by plasma surface treatment of the substrate to form a hydrophilic group such as a hydroxyl group. The plasma surface treatment may use oxygen plasma.

In the step of treating the silylating agent on the plasma surface-treated substrate, the plasma surface-treated substrate may be treated with a silylating agent to form an amine-functionalized substrate. For example, after immersing the plasma surface-treated substrate in an organic solvent, a silylating agent is added for at least 10 minutes; 1 hour or more; or reflux for at least 6 hours. The immersion is performed by immersing the substrate in the organic solvent, and at room temperature to 40° C. for 1 minute or more; more than 5 minutes; Alternatively, it may be performed while sonicating for 1 minute to 1 hour.

The organic solvent is a polar protic solvent such as methanol ethanol, propanol toluene, chloroform, dimethylformide ( N,N- dimethylformaide, DMF), tetrahydrofuran, carbon tetrachloride, benzene, etc.; It may include at least one selected from the group consisting of a polar aprotic solvent, a non-polar protic solvent, and a non-polar aprotic solvent, but is not limited thereto.

The silylating agent is the aminosilane compound, and the aminosilane compound is N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trime Toxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, (3-aminopropyl)trimethoxysilane ((3-Aminopropyl)trimethoxysilane; APS), (3-aminopropyl)trieth It may include at least one selected from the group consisting of oxysilane ((3-Aminopropyl)triethoxysilane) and N-(3-aminopropyl)-dimethyl-ethoxysilane, but is not limited thereto.

The step of contacting the substrate treated with the silylating agent with the metal salt solution may include contacting the substrate with the metal salt solution to form a metal-ion coated substrate. Put the substrate in a metal salt solution for at least 10 minutes; more than 30 minutes; Alternatively, it may be refluxed for 1 hour or more.

The metal salt solution includes a metal salt and an organic solvent containing zinc, cobalt or both, for example, the metal salt is a chloride, a nitrate, a nitrite, a sulfate, It may be acetate, sulfite, acetylacetonate, hydroxide, etc., but is not limited thereto. The organic solvent may be methanol, ethanol, isopropyl alcohol, or the like.

In the step of synthesizing and growing ZIF by contacting the substrate with the imidazole compound solution, the metal-ion-coated substrate is placed in an imidazole compound solution and ZIF is synthesized and grown on the substrate while stirring at room temperature to 40 ° C. can

The imidazole compound is 2-ethylimidazole, 2-decylimidazole, 2-hexylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptanedecylimidazole. , 1,4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2-methyl imidazole, 1-benzyl-2 -phenyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-undecyl imidazole and 1-cyano It may include at least one selected from the group consisting of ethyl-2-phenyl imidazole.

The imidazole compound solution contains an organic solvent, and may be, for example, methanol, ethanol, isopropyl alcohol, or the like.

Example

Synthesis of ZIF-67 and ZIF-8 crystals

(1) ZIF-67

0.9 g (3.1 mmol) of Co(NO ₃ ) ₂ .6H ₂ O and 1.0 g (12.2 mmol) of 2-methylimidazole were separately dissolved in an Erlenmeyer flask containing methanol (50 mL each). Then, the Co ²⁺ solution was poured into a 2-methylimidazole solution, and the mixture was lightly stirred with a magnetic bar at room temperature for 12 hours. After purple ZIF-67 crystals were formed, the solution was centrifuged at 8000 rpm for 10 minutes, and the crystals were washed 5 times with methanol.

(2) ZIF-8

Using the same method as ZIF-67, as a ^{Zn 2+} source instead of _{Co(NO 3} ) ₂ .6H _{2 O} A white crystalline precipitate was obtained using 1.0 g (3.1 mmol) of Zn(NO ₃ ) ₂ .6H _{2 O.} (a) XRD patterns, (b) SEM images, and (c) BET surface areas of the prepared ZIF-8 and ZIF-67 were measured and shown in FIG. 2 .

FIG. 2 shows (a) XRD patterns, (b) SEM images, and (c) BET surface areas of ZIF-8 and ZIF-67 prepared in Examples of the present invention according to an embodiment of the present invention. In Fig. 2(a), peaks consistent with the simulated patterns for the sodalite structures of ZIF-8 and ZIF-67 are shown. In the SEM image of FIG. 2(b), it can be confirmed that the rhombic icosahedron has a surface of ~0.5 μm and ~2 μm, and a sharp edge, respectively.

The porosity of the ZIF structure was confirmed in the revealing Type-I hysteresis loop (N ₂ gas adsorption: 77 K)). Brunauer-Emmett-Teller (BET) surface areas of ZIF-8 and ZIF-67 are 1887 and 2126 m ² ·g ^{-1 ,} respectively.

ZIF-8 and ZIF-67 are isostructural but contain different central metal ions (i.e., Zn ²⁺ and Co ²⁺ ) and have large pores (11.6 Å diameter) connected through small pores (3.4 Å width). can Since these pores are large enough for CEES molecules to access the pores, and the inner pores exhibit strong hydrophobicity, hydrophobic CEES molecules in polar media can be selectively adsorbed inside the pores.

CEES Removal Experiment

To investigate how effectively ZIF-67 and ZIF-8 adsorbed CEES, CEES (2.5 μl) was injected into sealed vials, each vial containing a water/ethanol mixed solution (1 mL), and The volume ratios of water to ethanol are 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 and 9:1, and ZIF particles (20 mg) are dispersed do. The vials were placed at 20 °C for 1 min for adsorption. For adsorption, the vial was held at 20 °C for 1 min, and a water/ethanol solution was used due to the low solubility of CEES and HD in pure water. After the capture process, the solution was filtered and the supernatant was diluted with acetonitrile. Finally, the removal amount of CEES was confirmed by analyzing the supernatant using gas chromatography (GC).

Reusability of ZIF-67

The reusability of ZIF-67 and ZIF-8 as adsorbents for HD/CEES was investigated in a water/ethanol mixture (9:1, v/v).

After the adsorption process, ZIF-67 and ZIF-8 were separated by centrifugation at 10,000 rpm for 10 minutes, and the obtained solid was regenerated by washing with pure acetonitrile and centrifuging to remove the adsorbed CEES.

During the second cycle, the adsorption process was performed again under the same conditions. Specifically, CEES (2.5 μl) was injected into a sealed vial containing 1 mL of a water/ethanol mixture (9:1, v/v) dispersed with regenerated ZIF particles (20 mg). The adsorption capacity was re-evaluated via GC analysis of the supernatant. This procedure was repeated 5 times to confirm the reusability of ZIF.

HD Removal Experiment

For removal of HD, the actual CWA, 20 mL of each ZIF-67 and ZIF-8 sample was suspended in 0.5 mL of 9: 1 and 5: 5 water/ethanol solutions, respectively. Then 1.5 μl of cyclohexanol (internal standard) and 2.5 μL of HD were added to the suspension. The mixture was stirred for 1 minute using a vortex mixer, centrifuged, and injected into a GC instrument to analyze the amount of CEES removed.

Figure 3 shows the total removal rate (solid dots), hydrolysis and adsorption of CEES in the presence of ZIF-8 (a) and ZIF-67 (b) prepared in the example of the present invention, according to an embodiment of the present invention; Selectivity is shown, and results are shown according to the volume fraction of ethanol (CEES: 2.5 mg, adsorbent: 20 mg) in a solvent at 25°C for 10 minutes. In FIG. 3 , the removal amount of CEES in the presence of ZIF-8 and ZIF-67 is determined by hydrolysis and adsorption according to various ratios of water/ethanol mixture (ratio: 10-100%, 1 minute at 20°C). When the water content is >50%, 90% or more (10% hydrolysis and 80% adsorption), it is removed within 1 minute in a water/ethanol mixed solution. All CEES is adsorbed quickly and completely in the ZIF, especially at 90% water content. ZIF materials can quickly and reliably remove toxic CEES or HD in polar solvents. ZIF-8 and ZIF-67 samples were extracted with acetonitrile after adsorption process and analyzed by GC. All samples recovered close to 95-100% of their initial dose. This is that ZIF-8 and ZIF-67 directly adsorb and store CEES molecules in the pores without any chemical reaction. In addition, it has a fast adsorption rate of less than 1 minute, showing the ability of ZIFs to remove HD in aqueous solution.

Figure 4 shows the total removal rate of CEES in the presence of ZIF-8 and ZIF-67 prepared in the example of the present invention, according to an embodiment of the present invention. Results according to (a) reaction time and (b) temperature in water/ethanol (1 mL, 9:1, v/v) at 25° C. for 5 minutes are shown (CEES: 2.5 mg, adsorbent sample: 20 mg) ).

In Fig. 4(a), the adsorption profile of ZIF-8 and ZIF-67 at 20 °C shows that CEES decreases with time. Nearly 100% of CEES was adsorbed within approximately 1 minute at 20 °C. Figure 4 (b) shows the temperature effect of ZIF-8 and ZIF-67 for CEES removal. CEES (2.5 mL), ZIF-8 or ZIF-67 (20 mg) and water/ethanol solution (9:1 (v/v)) were used for 1 min at 5, 10, 20 and 30° C. Temperature There is almost no effect on , and the removal rate of all samples is >95%.

Figure 5 shows the adsorption isotherms and model fitting results of (a) ZIF-8 and (b) ZIF-67 prepared in Examples of the present invention, according to an embodiment of the present invention, and the initial CEES concentration 10-370 mg/L and 25 °C for 5 min in water/ethanol (1 mL, 9:1, v/v).

5, the maximum adsorption capacity of ZIF-8 and ZIF-67 for CEES was 456.61 mg g ^-1 and It is 463.30 mg·g ^-1 . ZIF-8 and ZIF-67 provide similar adsorption performance and properties, and the adsorption performance is affected by the pore structure and hydrophobicity.

FIG. 6 shows the reusability of ZIF-8 and ZIF-67 for CEES adsorption prepared in the example of the present invention, according to an embodiment of the present invention. ethanol (1 mL, 9:1, v/v) (CEES: 2.5 mg, adsorbent: 20 mg).

ZIFs according to the present invention can be extracted stably and simply by washing the CEES adsorbed on the internal pores with acetonitrile. This is because it has an affinity between ZIF pores and acetonitrile and high solubility of CEES in acetonitrile. CEES-adsorbed ZIF was stirred and centrifuged in pure acetonitrile for 10 min. In order to completely extract CEES, it was repeated several times using pure acetonitrile. It can be seen from FIG. 6 that the ZIF particles maintain 95% or more of their initial adsorption capacity after 5 adsorption and desorption rotations. The high adsorption capacity, fast adsorption kinetics and easy regeneration and reuse of ZIF particles can provide suitable performance for application in large-scale HD detoxification process.

7 shows the removal rate, hydrolysis and adsorption amount of CEES for the adsorbents and various adsorbents prepared in Examples of the present invention, according to an embodiment of the present invention, at 25 ° C. for 10 minutes (CEES: 2.5 mg , adsorbent: 20 mg), in water/ethanol (1 mL, 9:1, v/v). In FIG. 7 , it can be seen that ZIF-8 and ZIF-67 have superior adsorption capacity compared to the conventionally known adsorbents such as activated carbon, silica, zeolite X, Y, A, and ZSM-5 in the adsorption capacity of CEES. In FIG. 7 , it can be seen that the removal rate of CEES is high in the order of ZIF-8 and ZIF-67 > ZIF-11 > activated carbon > ZSM-5 > zeolite X > zeolite Y > zeolite A.

In addition, it can be seen that the degree of CEES adsorption including hydrolysis was high in the order of ZIF-8 and ZIF-67 > activated carbon > ZSM-5 > ZIF-11 > silica > zeolite X > zeolite Y > zeolite A.

Figure 8 shows the total removal rate for actual HD according to the reaction time in the presence of ZIF-8 and ZIF-67 prepared in the Example of the present invention according to an embodiment of the present invention, and the removal test conditions are, 25° C., water/ethanol (1 mL, 9:1 or 5:5 v/v), HD: 2.5 mg and adsorbent: 20 mg. In FIG. 8, it can be seen that ZIF-8 and ZIF-67 removed 100% HD from a water/ethanol solution (9:1, v/v) within 1 minute. It has very good HD adsorption performance (nearly 90%, 1 min) to ZIF-8 and ZIF-67 in a water/ethanol mixture 5:5 (v/v), similar to CEES without hydrolysis. Moreover, no product by hydrolysis of HD was found in GC analysis. This shows that ZIF-8 and ZIF-67 are capable of real CWA removal.

Synthesis of ZIF-8 and ZIF-67 on the face

It was synthesized according to the preparation method of ZIF-8 and ZIF-67/cotton complexes shown in FIG. 9 .

The prepared square face (2 cm × 2 cm) _{was treated with O 2} plasma to remove organic contaminants, and hydroxyl groups were generated. The cleaned cotton squares were then introduced into a two-necked round bottom flask (100 mL), then evacuated under vacuum ^{at less than 10 -2} torr for 2 hours and filled with high purity argon. Dry toluene (50 mL) was added to the flask and sonicated for 5 minutes to soak the noodles in toluene. After the addition of 3-aminopropyl trimethoxysilane (0.5 mL) as a surface-silylating agent, the mixture was refluxed for 6 hours with continuous stirring. The reactor was then cooled to room temperature and washed with fresh toluene to completely remove excess surface-silylating agent. After washing, the surface-modified cotton squares were dried under vacuum for 20 minutes. Next, amine-functionalized cotton squares were separately added to vials containing zinc acetate (zinc acetate, 10 mM) or cobalt acetate (10 mM) ethanol solutions for 1 h after refluxed while The metal-ion-coated cotton squares were then washed with a large amount of fresh ethanol. Next, 5 pieces of each type of cotton were placed in a vial containing 1,4-methylimidiazole (1,4-methylimidiazole, 0.06 mol, 0.06 g), dissolved in methanol (5 mL), and warmed for 6 h. stirred vigorously.

For ZIF-67, 1.484 g of Co(NO ₃ ) ₂ .6H ₂ O was first dissolved in 50 mL of methanol (solution A), and separately 3.278 g of 1,4-methylimidiazole (1,4- methylimidiazole) was dissolved in 50 mL of methanol (solution B). After the treated cotton pieces were immersed in solution A, solution B was slowly poured into solution A with stirring at 200 rpm at room temperature (25±3° C.) for 6 hours. The cotton sample was then separated from the colloidal dispersion and washed three times with MeOH. Finally, the obtained product was dried in air for subsequent characterization.

10 is a (a) image, (b) SEM image (c) of ZIF-8 and ZIF-67 grown on the cotton prepared in the example of the present invention, and pure cotton according to an embodiment of the present invention; The XRD pattern is shown. ZIF-8 and ZIF-67 complexes formed by site-directed growth using cotton as a scaffold. ZIF-8 or ZIF-67 nuclei are introduced onto the cotton substrate, and the surface of the cotton is modified by amine functional groups. That is, growth of ZIF-67 on cotton was treated with imidazole to form a ^{Co 2+-} imidazole complex on the surface of the surface in which ^{Co 2+ ions were coordinated to the modified amine group.} The color of the ZIF-67-coated cotton changed from white to dark purple after growth, Fig. 10(a) shows that the pure cotton had a smooth surface, and the ZIF-67/cotton composite was coated with ZIF-67 to make it rough. represents the surface. In particular, the ZIF-67/cotton composite can confirm the growth of well-dispersed ZIF-67 nanocrystals on the cotton surface.

11 shows the removal test process of CEES using (a) ZIF-8-coated side and ZIF-67-coated side prepared in Example of the present invention, according to an embodiment of the present invention; (b) A plot of CEES extracted from each side sample and remaining on glass.

CEES (2.5 μl) was sprayed between two glass slides and each covered the ZIF-8 cotton complex and ZIF-67/cotton complex soaked in water/ethanol (9:1, v/v) solution for 1 min. In order to analyze the compounds remaining in each of the glass substrate and the composite, 9:1 (v/v) water/ethanol solution was additionally introduced to wash the composite, and each supernatant was analyzed using GC. The GC spectrum of the washing solution did not show any peaks for hydrolysis products related to CEES or CEES anion, and almost all products (97%) were recovered by washing with pure organic solvent. In addition, ZIF-8 and ZIF-67 showed the same effect. To evaluate the functionality of ZIF-functionalized cotton, pure untreated cotton was tested in the same manner. After covering the CEES contaminated glass slide for 1 minute, 20% of the initial amount of CEES remains on the glass substrate in its original and hydrolyzed form, and the remaining 80% is on the cotton as CEES and its hydrolyzed form. adsorbed. That is, when using the ZIF-8 cotton composite and the ZIF-67/cotton composite, adsorption close to 100% can be achieved by wiping a specific substrate contaminated with mustard gas molecules.

As a result, the present invention prepared two isostructural ZIF-8 and ZIF-67, and ZIF-8 or ZIF-67-plane composites to rapidly adsorb and remove the chemical agent mustard gas (HD). Because HD is highly toxic, 2-chloroethyl ethyl sulfide (CEES), an HD simulator, was used to understand the effect of solvent polarity on adsorption. In addition, CEES and Real HD were adsorbed and removed from aqueous solutions using ZIF-8 or ZIF-67. The adsorption capacity of ZIF-8 and ZIF-67 was correlated with the polarity and composition of the solvent, in a 9: 1 (v/v) water/ethanol solution and 97% CEES (2.5 μl in 1 mL) within 1 min at 25 °C was rapidly adsorbed by ZIF-8 and ZIF-67. In addition, ZIF-8 and ZIF-67 were successfully synthesized on the surface, and more than 95% of contaminants could be removed from the substrate contaminated with HD simulant. In addition, the present invention may provide a variety of articles that can defend, protect, remove and/or treat mustard gas using these properties.

As described above, although the embodiments have been described with reference to the limited embodiments and drawings, various modifications and variations are possible from the above description by those skilled in the art. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (17)

Zeolitic imidazolate framework (ZIF)-8 and ZIF-67;
It has the function of adsorption of chemical agent molecules in a moisture environment,
The moisture environment, 50% or more; 70% or more; or in an aqueous solution containing at least 80% water,
The chemical agent is a blister agent,
A chemical agent adsorbent composition.
According to claim 1,
80% or more of the total removal rate of the chemical agent is due to the adsorption function of the chemical agent adsorbent,
A chemical agent adsorbent composition.
delete delete materials; and
ZIF-8, ZIF-67 or both coated on the substrate;
including,
The ZIF-8, ZIF-67 or both are nanocrystals,
The ZIF-8, ZIF-67 or both are synthesized and coated on the substrate,
Wherein the substrate is surface-treated with a silylating agent prior to the synthesis of ZIF-8, ZIF-67 or both,
A ZIF-based complex with the ability to adsorb chemical agent molecules in a moisture environment.
a substrate coated with ZIF-8; and
a substrate coated with ZIF-67;
including,
The ZIF-8, ZIF-67 or both are synthesized and coated on the substrate,
Wherein the substrate is surface-treated with a silylating agent prior to the synthesis of ZIF-8, ZIF-67 or both,
A ZIF-based complex with the ability to adsorb chemical agent molecules in a moisture environment.
6. The method of claim 5,
Wherein the ZIF-8, ZIF-67 or both are included in 0.01 wt% to 30 wt% of the substrate,
ZIF-based complex.
6. The method of claim 5,
The substrate will include fibers, fabrics, or both,
ZIF-based complex.
The ZIF-based complex of claim 5 or 6;
including,
An article having a chemical agent molecule adsorption function.
10. The method of claim 9,
wherein the article is a protective garment, a gas mask, a mask, a filter, a glove, a garment, a sheet, a film or a mat,
article.
preparing a substrate;
Plasma surface treatment on the substrate;
treating a silylating agent on the plasma surface-treated substrate;
contacting the substrate treated with the silylating agent with a metal salt solution; and
synthesizing and growing a Zeolitic imidazolate framework (ZIF) by contacting the substrate with an imidazole compound solution;
including,
The ZIF, including ZIF-8, ZIF-67 or both,
A method for preparing ZIF-based complexes for adsorption of chemical agent molecules.
delete 12. The method of claim 11,
The substrate will include fibers, fabrics, or both,
A method for preparing a ZIF-based composite.
14. The method of claim 13,
The fiber is, pulp, hemp fiber, cotton, hemp, wool, silk, cellulose, polyamide (polyamide), acrylic (acrylic), vinyl nylon (vinyl-nylon), polyester, polyimide (polyimide), aramid (aramid) ), polyethylene (poly etylene), polyethylene terephthalate (polyethylene terephthalate), polylactic acid (polylactic accid) and that comprising at least one selected from the group consisting of nylon,
A method for preparing a ZIF-based composite.
12. The method of claim 11,
The silylating agent is an aminosilane compound,
The aminosilane compound is N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, N-2-(aminoethyl) -3-Aminopropyl triethoxysilane, (3-aminopropyl) trimethoxysilane ((3-Aminopropyl) trimethoxysilane; APS), (3-aminopropyl) triethoxysilane ((3-Aminopropyl) triethoxysilane) and N-(3-aminopropyl)-dimethyl- which comprises at least one selected from the group consisting of ethoxysilane,
A method for preparing a ZIF-based composite.
12. The method of claim 11,
The metal salt solution, comprising a metal salt and an alcohol solvent,
A method for preparing a ZIF-based composite.
12. The method of claim 11,
The imidazole compound is 2-ethylimidazole, 2-decylimidazole, 2-hexylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptanedecylimidazole. , 1,4-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2-methyl imidazole, 1-benzyl-2 -Phenyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-undecyl imidazole and 1-cyano Which comprises at least one selected from the group consisting of ethyl-2-phenyl imidazole,
A method for preparing a ZIF-based composite.

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