KR20180115494A - Surface modified metal organic franeworks for removal of toxic gases - Google Patents

Abstract

The present invention relates to surface-modified metal organic frameworks. More specifically, the present invention relates to surface-modified metal organic frameworks in which a basic amine compound is deposited on a surface of the metal organic frameworks and the inside of a pore or is coupled to the inside of a frame. The surface-modified metal organic frameworks have a detoxification effect capable of removing a toxic gas in the air by adsorbing and decomposing the toxic gas. The amine compound is composed of 3 to 30 wt% based on the entire 100 wt% of the metal organic frameworks.

Description

{SURFACE MODIFIED METAL ORGANIC FRANEWORKS FOR REMOVAL OF TOXIC GASES FOR TOXIC GAS REMOVAL}

The present invention relates to a surface-modified metal organic material as a reactive material having detoxification effect capable of adsorbing, decomposing and removing toxic gases in the air.

Filtering devices that protect individuals or groups to safely breathe in toxic chemicals, especially those that are contaminated with chemical agents, are now used with filters filled with activated carbon based filtration materials. These filters have a simple structure, in which the filter material is filled in the housing and the housing, and the contaminated air passes through the layer filled with the filter material, and contacts with the filter material, whereby toxic gaseous materials are separated by physical or chemical adsorption It is the principle to be removed.

In the general purpose respirator for purifying chemical agents, metal salts such as copper, zinc, molybdenum and the like are impregnated with activated carbon, and in US Patent No. 4,802,898, cyanogen chloride (hereinafter referred to as " (Hereinafter also referred to as " TEDA ") is added to increase the ability to remove gas.

However, ASZM-TEDA, which is an active chemical protecting agent for chemical agents, has excellent filtration performance to remove chemical agents, but has a limited number of filtrate water. In particular, cyanide chloride (CK) as a blood agonist is a metal salt impregnated on activated carbon, (TEDA) and so on, the lifetime of the adsorbent is extremely limited.

In addition, recently, counter-terrorism operations and large-scale chemical accident accidents are included in the military's duties. Therefore, industrial toxins such as hydrochloric acid (HCl), hydrofluoric acid (HF) (SO ₂ ), ammonia (NH ₃ ), nitrogen dioxide (NO ₂ ) and formaldehyde (HCHO) are increasing in the case of activated carbon based military activated carbon. However, existing activated carbon based military activated carbon has limited protection against these industrial toxic substances .

U.S. Patent No. 8,877,677 discloses that TEDA is deposited on zirconium hydroxide (Zr (OH) ₄ ) particles, which are inorganic materials, or TEDA and metal salts such as copper and zinc are simultaneously impregnated to enhance resistance to acid gas including CK.

However, in these cases, since the specific surface area of zirconium hydroxide (Zr (OH) ₄ ) itself is smaller than that of activated carbon, it lacks the physical adsorption capability for chemical agents such as sarin and the like. The activated carbon can not be used in place of the activated carbon which is exposed to the actual environmental conditions.

Therefore, it is necessary to develop a new concept of adsorbent material which can remove chemical agents with relatively high molecular weight such as nerve gas and industrial materials of toxic gas including acidic and basic gas at the same time and overcome the influence of moisture in the air.

Metal organic frameworks (MOF) are also commonly referred to as " porous coordination polymers ", or " porous organic-inorganic hybrid materials " or " metal organic frameworks ".

The metal organic layer has recently started to develop by the combination of molecular coordinate bonding and material science. The metal organic layer has nano-sized pores and thus provides a high surface area. Therefore, Examples of applications for carrying and delivering the composition include those that are mainly used for adsorbents, gas storage materials, sensors, membranes, functional thin films, drug delivery materials, catalysts and catalyst carriers, Or can be used to separate molecules by size using pores.

Despite these advantages, however, there are many limitations in application due to the disadvantage that the structure of the skeleton is destroyed upon contact with moisture. In addition, even if it is intended to be used for a filter or the like, there is a severe restriction on conditions such as minimizing contact with moisture in the air. Therefore, despite the many advantages, metal organic membranes have not yet been used for the decontamination and filtration of chemical solvents.

U.S. Patent No. 4,802,898 U.S. Patent No. 8,877,677

As noted above, there are some problems with military activated carbon, which have limited ability to adsorb some chemical agents and toxic industrial materials, and industrial toxic gases including acid gases, but have little effect on chemical agents The problem of zirconium hydroxide (Zr (OH) ₄ ) impregnated with triethylenediamine (TEDA), and the problem of the conventional metal organic component which is vulnerable to moisture in the air are solved at the same time.

Accordingly, the present invention provides a metal organic compound having a large specific surface area and high resistance to humidity, heat, and chemical resistance, and a basic amine compound is deposited on the pores of the metal organic compound to provide a surface modified metal organic compound, And a multifunctional adsorbent material capable of simultaneously removing toxic gases such as industrial materials, and the like.

In order to accomplish the above object, the present invention provides a metal organic substrate having an amine compound deposited on the surface and pores of metal organic franeworks, And 3 to 30% by weight, based on 100% by weight, of a surface modified metal organic material for removing toxic gases.

The metal organic layer is formed of a metal having a central metal such as zirconium (Zr), iron (Fe), titanium (Ti), copper (Cu), hafnium (Hf), vanadium (V), zinc (Zn), cobalt (Ni), barium, calcium, strontium, niobium, chromium, tantalum, molybdenum, rubidium, osmium, tungsten, (W), Mn, Rd, Pd, Pt, Ag, Au, Y, Ge, As, which contains at least one of metal ions of lead (Pb), indium (In), gallium (Ga), antimony (Sb) and derivatives thereof.

Specifically, the metal organic meta than the _{MOF-808 (Zr 6 O 4} (OH) 4 (BTC) 2 [HCOO] 6), UiO-66 (Zr 6 O 4 (OH) 4 (BDC) 6), UiO- _{66-NH 2 (Zr 6 O} 4 (OH) 4 (BDC-NH 2) 6), UiO-67 (Zr 6 O 6 (BPDC) 12), UiO-67-NH 2 (Zr 6 O 6 (BPDC- NH ₂ ) ₁₂ and MIL-100 (Fe) (Acid-activated Fe ₃ O (H ₂ O) ₃ F (BTC) ₂ ) In addition to the metal organic layer, a variety of metal organic layers can be used as is commonly known to those skilled in the art.

'BDC' in the chemical formula representing the structure of the above metal organic device means 1,4-benzenedicarboxylate, 'BPDC' means 4,4'-biphenyldicarboxylate Refers to 4,4'-biphenyldicarboxylate, and 'BTC' refers to 1,3,5-benzenetricarboxylate.

The amine compound may be any one selected from the group consisting of triethylenediamine, triethylamine, quinuclidine, and pyridine-4-carboxylic acid, or a mixture thereof Can be used.

Preferably, the surface-modified metal organic material is surface-modified by a rotary evaporation method using a rotary evaporator or a vacuum evaporation method using a vacuum evaporator, and in particular, a metal organic material surface-modified by a vacuum deposition method is used for removing toxic gases It is easier.

The surface modified metal organic material may have a breakthrough time of 1000 min / g or more by weight of the toxic gas, and preferably 1000 min / g to 3500 min / g. In wet conditions where the relative humidity in the air is about 60% at 20 to 30 占 폚 at room temperature, the weight of the toxic gas using the metal-organic modified surface of the modified surface is about three times longer than that of the toxic gas. The removal performance of the cleaning solution is further improved. Such breakthrough time does not deteriorate the adsorption and decomposition performance when compared with conventional antiseptics such as ASZM-TEDA activated carbon, and has further improved effect.

In addition, the toxic gas to be removed by the surface modified metal organic material of the present invention is at least one selected from cyanogen chloride, dimethyl menthylphosphonate, ammonia and sulfur dioxide, Chemical warfare agent chemical agents and gaseous acidic, basic and neutral toxic industrial compounds (TIC).

The metal organic material according to the present invention can be used in products for adsorbing and decomposing toxic gases, and can be applied to products such as, for example, sanitary pads for respirators, filters, and protective materials.

The metal organic material having the surface modified by deposition of the basic amine compound on the metal organic material of the present invention has the effect of drastically improving the ability to simultaneously adsorb and remove chemical agents and toxic industrial materials not possessed by existing adsorbents .

In addition, it is possible to secure an equivalent effect in a small amount, and the weight of protective equipment for toxic gases can be remarkably reduced by using materials that are lighter than existing adsorbent materials, so that the gas- And materials such as protective materials can be utilized in various ways.

1 is a graph showing nitrogen adsorption isotherms before and after deposition of triethylenediamine (TEDA) on MOF-808 by rotary evaporation according to an embodiment of the present invention.
FIG. 2 is a graph showing nitrogen adsorption isotherms before and after deposition of triethylenediamine (TEDA) on MOF-808 by a vacuum deposition method according to an embodiment of the present invention.
FIG. 3 is an X-ray diffraction analysis (XRD) graph of Example 4 and Example 5 of a metal organic surface modified by a vacuum deposition method according to an embodiment of the present invention.
4 is a graph showing breakthrough curves of cyanide (CK) for adsorbents.
FIG. 5 is a graph comparing the deposition amount of triethylenediamine (TEDA) and the adsorption performance of cyanide chloride (CK) according to the deposition method.
FIG. 6 is a graph comparing breakthrough curves of chlorinated cyan (CK) with respect to MOF-808-TEDA according to air humidity conditions.
FIG. 7 is a graph comparing breakthrough curves of cyanide (CK) with respect to UiO-66-TEDA according to air humidity conditions.
8 is a graph showing breakthrough curves of dimethylmeththylphosphonate (DMMP) for surface-modified metal organic particles according to the present invention.
9 is a graph showing a breakthrough curve of ammonia (NH ₃ ) as a basic gas for a surface-modified metal organic material according to the present invention.
10 is a graph comparing breakthrough curves of SO ₂ , an acid gas, with ASZM-TEDA and MOF-808-TEDA 30%.

Hereinafter, a surface modified metal organic material having an admiral effect capable of adsorbing, decomposing and removing toxic gases in the air to be carried out through the present invention will be described in detail with reference to the following Examples. However, these examples are for illustrative purposes only, and the present invention is not limited to these examples.

The surface-modified metal organic component of the present invention can be obtained by reacting a metal organic component named MOF-808, UiO-66 and MIL-100 (Fe) with a basic amine compound using triethylenediamine (TEDA) The surface is modified in the manner described.

Meanwhile, the manufacturing conditions such as rotation speed, rotation time, temperature, drying temperature and drying time in the rotary evaporation method and the vacuum deposition method performed by the method of manufacturing the surface modified metal organic material of the present invention are repeatedly performed The optimum condition is obtained experimentally and the conditions considered to be optimal for the purpose of the present invention are described.

Example 1 is a modification of the surface of an amine compound in a metal organic phase using a rotary evaporation method, in which a metal organic MOF-808 powder and an amine-based compound triethylenediamine (TEDA) powder were mixed with a rotary evaporator ) At a temperature of 60 ° C under atmospheric pressure, while rotating at a rotational speed of 10 to 120 rpm, preferably 30 to 80 rpm, at a normal pressure for 2 to 24 hours, And triethylenediamine (TEDA), which is an amine compound, is deposited on the surface by sublimation, in which 10 wt% of triethylenediamine (TEDA) is deposited.

Example 2 and Example 3 were prepared by the same rotary evaporation method as in Example 1 except that the amount of triethylenediamine (TEDA) deposited on the pores and the surface of MOF-808 was 15 By weight (Example 2) and 20% by weight (Example 3).

Example 4 is a modification of the surface of an amine-based compound by a vacuum deposition method in a metal organic furnace. A container containing MOF-808 powder containing metal organics was connected to a pump capable of vacuum treatment, (TEDA) powder, and the triethylenediamine (TEDA) container was added in a stepwise manner from 50 to 170 ° C by passing through another connecting port and a container containing an amine compound, triethylenediamine To allow sublimed triethylenediamine (TEDA) to deposit on the pores and surfaces of MOF-808. After sufficient deposition, the container containing MOF-808, which is a metal organic material, was vacuum-treated again, so that excess triethylenediamine (TEDA) on the surface of the metal organic material was removed to obtain 29 wt% of triethylenediamine (TEDA) To be deposited.

In Example 5, a surface-modified metal organic layer was prepared by the same vacuum deposition method as in Example 4, except that 30 wt% of triethylenediamine (TEDA) was deposited on the pores of the MOF-808 and the surface thereof.

The surface area of the MOF-808 surface-modified metal organic particles and the surface-modified metal organic particles before surface modification in Examples 1 to 5 was measured at -196 占 폚 The surface area before and after the deposition of triethylenediamine (TEDA) on the metal organic particles was measured by measuring the physical adsorption amount of nitrogen within the range of 1 atm and the boiling point of nitrogen. The results are shown in Table 1, Fig. 1 and Fig. 2, and the BET specific surface area results are shown in units of m ² / g in terms of surface area per weight.

division Material type TEDA deposition amount
(weight%) Deposition method Specific surface area
(m ² / g) MOF-808 0 - 1,612 Example 1 MOF-808-TEDA 10 Rotary evaporation 1,176 Example 2 MOF-808-TEDA 15 Rotary evaporation 540 Example 3 MOF-808-TEDA 20 Rotary evaporation 337 Example 5 MOF-808-TEDA 30 Vacuum deposition 1,024

As shown in Table 1, the specific surface area of the surface-modified metal organic material of Example 1 in which 10 wt% of triethylenediamine (TEDA) was evaporated by the rotary evaporation method was 1,176 m ² / g, The specific surface area of Example 5, in which the diamine (TEDA) was 30 wt% surface modified, was shown to be 1,024 m ² / g, which means that the specific surface area of the MOF-808 metal oxide before surface modification was 1,612 m ² / g, the specific surface area did not decrease significantly.

FIG. 1 shows the results of nitrogen adsorption isotherm comparative analysis of MOF-808, which is a surface-modified metal organic material according to Examples 1 to 3 and a metal organic material before surface modification. As shown in FIG. 1, In Example 2 and Example 3 in which the amount of triethylenediamine (TEDA) deposited was increased to 15 wt% and 20 wt%, the specific surface area of triethylenediamine (TEDA) was increased to 540 m ² / g and 337 m ² / (TEDA), the specific surface area was reduced by surface modification. As can be seen from Table 1, triethylenediamine (TEDA) was deposited in a smaller amount than Example 5, but showed a smaller specific surface area.

And FIG. 2 shows the results obtained by using the vacuum deposition method in which the metal organic particles of which the surface was modified to 29 wt% and 30 wt% of triethylenediamine (TEDA), respectively, and Example 4 and Example 5, (TEDA) as shown in FIG. 2, the specific surface area is decreased. This is because the surface area of the metal organic particles of Example 1 And the decrease in the specific surface area was smaller than that in Example 3.

In addition, although the results of measuring the pore size in this specification are not shown in the drawings of the present invention, the MOF-808 The volume of the mesoporous pores in the vicinity of the diameter of 2 nm contained in the structure was maintained at about 50% without much decrease, and it was confirmed that the active surface for removing toxic chemicals was further activated.

Therefore, it is preferable to use a vacuum evaporation method using a vacuum evaporator rather than a rotary evaporation method using a rotary evaporator as a method of surface modification with triethylenediamine (TEDA), which is an amine compound.

As a result of X-ray diffraction analysis (XRD) of Example 4 and Example 5, which were surface-modified metal organic materials by a vacuum deposition method, as shown in FIG. 3, It was confirmed that the crystal structure of the organic layer did not change much before and after the deposition.

The smaller the change in crystallinity measured in the X-ray diffraction analysis, the smaller the surface area and the decrease in the pore volume. The lower the surface area of the metal organic layer, the lower the surface area and the higher the content of triethylenediamine (TEDA) As shown in Fig.

In order to confirm the adsorption and decomposition effects of various toxic gases on the surface-modified metal organic particles of the present invention, the penetration tests by toxic gases were carried out in the same manner as in Examples 6 to 9.

In Example 6, to evaluate the adsorption performance of cyanide chloride (CK) of powder-type surface-modified metal organic particles prepared by the same method as the above Examples 1 to 5, the particles were molded into pellets, And particles having a size of 212 to 250 탆 (60 to 70 mesh) were selected as the particle size at which the pressure drop in the adsorption reactor can be minimized. The surface-modified metal organic material is charged into a 4 mm diameter glass tube with an adsorption reaction tube so that the filling height is about 8 cm with a filling amount of 0.1 ml.

For the breakthrough of cyanogen chloride (CK), wet air with a relative humidity of 60% was passed through the reaction tube filled with the surface-modified metal organic material for 2 hours at 20 ° C and relative humidity of 60 % Of cyanogen chloride (CK) concentration of 4,000 mg / m ³ was fed to the inlet of the adsorption reactor at a linear velocity of 2.65 cm / sec.

In order to compare the adsorption performance with conventional adsorbents for cyanide chloride (CK), ASZM-TEDA, zirconium hydroxide (Zr (OH) ₄ ) of Calgon, USA and Zr (OH) ₄ deposited with 6 wt% triethylenediamine ) ₄ -TEDA and UiO-66-TEDA 6 wt% triethylenediamine (TEDA) deposited on a metal organic UiO-66 were subjected to a breakthrough test of CI chloride in the same manner as in Example 6. [

The concentration of chlorinated cyanide (CK) was measured in real time at the front and rear ends of the adsorption reaction tube filled with the metal organic surface-modified with the adsorbent, and the adsorption reaction tube outlet concentration (C) The results are shown in Table 2 and Fig.

Material type Maximum TEDA deposition amount (wt%) Charge amount
(g / 0.1 ml) Break-out time
(minute) Break-through time
(Min / g) ASZM-TEDA 3.5 0.055 59 1,073 Zr (OH) _4- TEDA 6 0.102 65 637 UiO-66 0 0.034 0 0 UiO-66-TEDA 6 0.027 44 1,630 MOF-808 0 0.056 0 0 MOF-808-TEDA 30 0.049 171 3,490

As can be seen from the results in Table 2, the breakthrough time of the chlorinated cyanide (MOF-808-TEDA) was the longest, indicating that the protection against chlorinated cyanide (CK) was the most excellent.

In addition, when the adsorbability is good, the concentration increases more slowly or slowly with respect to the adsorption time at the breakthrough curve, and when the adsorption performance deteriorates, the concentration of the breakthrough curve increases sharply.

Based on these points, it can be seen from Table 2 and FIG. 4 that the filling density of MOF-808-TEDA is lower than that of Zr (OH) ₄ -TEDA or ASZM-TEDA, Was about 3.3 times longer than ASZM-TEDA and 5.5 times longer than Zr (OH) ₄ -TEDA. The performance of UiO-66-TEDA was 1.5 times higher than that of ASZM-TEDA and 2.5 times higher than that of Zr (OH) ₄ -TEDA. These results imply that the weight of the adsorbent can be drastically reduced when designing a filtration device for the same protection.

FIG. 5 is a graph showing a comparison between the method of depositing triethylenediamine (TEDA) on the MOF-808 metal organic compound and the adsorption capacity of cyanide chloride (CK) according to the deposition amount.

As shown in FIG. 5, when triethylenediamine (TEDA) was deposited on MOF-808 at atmospheric pressure, when the amount of triethylenediamine (TEDA) was 15 wt% (MOF-808-T15) And the adsorption performance of cyanide chloride (CK) was confirmed.

This is the Table 2 above, and we have seen in Figure 4, as a commercial product, ASZM TEDA-activated carbon or Zr (OH) _4, if the adsorption performance of the best visible -TEDA cyan chloride (CK) triethylenediamine (TEDA) deposition amount of 6% by weight, that (TEDA) was deposited at a concentration of 15% by weight in the case of MOF-808.

Further, when 15% by weight of triethylenediamine (TEDA) was vapor-deposited by rotary evaporation at normal pressure (MOF-808-T30V) in the case of vapor deposition of triethylenediamine (TEDA) -808-T15) than that of the conventional cyanide (CK) adsorbing ability. This is because when triethylenediamine (TEDA) is deposited evenly on the pore inner surface of MOF-808 when it is deposited in a vacuum environment, triethylenediamine (TEDA) deposited on a wide surface can effectively react with cyanide .

In order to examine the effect of air humidity on the removal ability of CI, the MOF-808-TEDA was mixed with 30 wt% of MOF-808-TEDA under the conditions of relative humidity of 0 and 60% And 6 wt% of UiO-66-TEDA are shown in Figs. 6 and 7, respectively. 6 and 7 show the results of experiments on the breakthrough of cyanide chloride (CK) in the case where the relative humidity of the air passing through the adsorption layer made of the metal organic substrate with the surface-modified triethylenediamine (TEDA) , And Humid shows the results of a breakthrough of cyanide chloride (CK) in the case where the relative humidity of air is 60%.

In general ASZM-TEDA activated carbon, the abrupt adsorption capacity deteriorates under high humidity conditions. However, as shown in FIGS. 6 and 7, the amine-based UDO-66-TEDA and MOF-808-TEDA (CK) breakthrough time was more than three times higher in a wet condition where the relative humidity was 60% than in a dry condition where the relative humidity was 0%. This result shows that the cyanide chloride CK) is improved, it can be seen that the use of the surface-modified metal organic material of the present invention is highly likely to take place in a humid field environment condition.

Example 7 was conducted in order to evaluate the adsorption performance of dimethylmethylphosphonate (DMMP) on the surface-modified metal organic framework with dimethylmeththylphosphonate (DMMP).

Here, dimethylmethylphosphonate (DMMP) is a similar agent to warin gas sarin (GB), which is adsorbed by an adsorbent in the same manner as sarin. Therefore, if the adsorption capacity of dimethylmethylphosphonate (DMMP) is good, it can be judged that the adsorption performance against sarin, which is a nerve gas, is also excellent.

Specifically, Example 7 was carried out in the same manner as in Example 6 with the surface-modified metal organic particles in the form of powder prepared in the same manner as in Example 5, except that dimethylmethylphosphonate (DMMP) Treated at a temperature of 23 to 27 ° C and a relative humidity of 10% for 2 hours to a reaction tube filled with the surface-modified metal organic material, and then dimethylethylphosphonate DMMP) concentration was 3,000 mg / m ³ of sending a mixed air to a linear velocity of 5.9 cm / sec to the adsorption reactor inlet perform the breakthrough experiment of dimethyl methyl phosphonate (DMMP).

As a result, as shown in FIG. 8, it was confirmed that the adsorption performance of dimethyl methylphosphonate (DMMP) was remarkably increased in MOF-808-TEDA than in MOF-808, In the case of MIL-100 (Fe) -TEDA whose surface was modified by depositing triethylenediamine (TEDA) on MIL-100 (Fe) as another metal organic material, dimethylmethylphosphonate DMMP). As a result, it can be understood that DMEM can be effectively reacted through surface modification with triethylenediamine (TEDA).

Example 8 is for evaluating the adsorption performance of ammonia (NH ₃ ), which is a basic gas of the surface-modified metal organic material, to a powder-form surface-modified metal organic material prepared in the same manner as in Example 5 with the sixth embodiment and performs the same way, except ammonia (NH ₃₎ to a surface-modified metal-organic meta is filled reaction tube to a breakthrough experiment with 23 to 27 ℃ temperature of ammonia (NH ₃₎ the concentration is 1,000 mg / m ³ of sending a mixed air to a linear velocity of 5.9 cm / sec to the adsorption reactor inlet was carried out to breakthrough test, wherein ammonia (NH ₃₎ 0% respectively, the relative humidity to determine the adsorption capacity according to the humidity and 80% And the wave breaking experiment was carried out.

As a result, as shown in FIG. 9, in the case of MOF-808-TEDA having a surface modified metal organic compound of the present invention, the ammonia (NH ₃ ) breakdown time was 70 minutes under a dry condition with a relative humidity of 0% The breakthrough time of ammonia (NH ₃ ) in the wet condition at 80% was 80 minutes. Although not shown in the figure, in the case of ASZM-TEDA activated carbon, the breakthrough time of ammonia (NH ₃ ) was 38 minutes and the relative humidity was 80% under a dry condition with a relative humidity of 0% .

Example 9 is for evaluating the adsorption performance against sulfur dioxide (SO ₂ ) which is an acid gas of a surface-modified metal organic material, and the surface-modified metal organic material prepared by the same method as in Example 5 was adsorbed The reaction tube was charged in a glass tube with an inner diameter of 4 mm to a filling amount of 0.5 ml and a filling height of about 4 cm, and a sulfuric acid gas (SO ₂ ) concentration of 525 ppm was measured at 20 ° C in the adsorption reaction tube filled with the surface- Nitrogen mixed gas was sent to the inlet of the adsorption reactor at a linear velocity of 5.3 cm / sec.

In order to compare the adsorption performance with sulfur dioxide (SO ₂ ), a commercial product, ASZM-TEDA activated carbon, was tested under the same conditions as in Example 9.

As a result, the breakthrough time of the acid gas is sulfur dioxide (SO ₂₎ in the surface-modified metal sulfur dioxide (SO ₂₎ in comparison to the organic freezing individual MOF-808-TEDA wt% ASZM-TEDA as shown in FIG. 10 And the adsorption performance was improved to about 2 times or more.

Therefore, as described above, the metal organic component surface-modified with the basic amine compound of the present invention is superior to the metal organic component before the surface modification or the conventional ASZM-TEDA and Zr (OH) ₄ -TEDA, The adsorbing and decomposing performance of various toxic gases such as dimethyl menthylphosphonate (DMMP), ammonia (NH ₃ ) and sulfurous acid gas (SO ₂ ) is not deteriorated, the adsorption and decomposition performance is remarkably improved, It can be used as a filtration material for military and industrial use because it can achieve not only a low adsorption performance but also an excellent adsorption performance as well as an effect equal to or greater than that of an adaptation amount by using lighter materials than conventional materials.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. It is clear that it is not. Accordingly, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (9)

An amine-based metal organic compound, which is deposited on the surface and pores of metal organic franeworks or bonded to the inside of the skeleton,
Characterized in that the amine-based compound comprises from 3 to 30% by weight, based on 100% by weight of the total of the metal organic components, of a surface-modified metal organic framework for the removal of toxic gases. The method according to claim 1,
The metal organic layer is formed of a metal having a central metal such as zirconium (Zr), iron (Fe), titanium (Ti), copper (Cu), hafnium (Hf), vanadium (V), zinc (Zn), cobalt (Ni), barium, calcium, strontium, niobium, chromium, tantalum, molybdenum, rubidium, osmium, tungsten, (W), Mn, Rd, Pd, Pt, Ag, Au, Y, Ge, Characterized in that it contains at least one metal ion selected from the group consisting of As, Pb, In, Ga, and Sb and derivatives thereof. . 3. The method of claim 2,
The metal organic meta removes toxic gas, characterized in that any one selected from the MOF-808, UiO-66, UiO-66-NH 2, UiO-67, UiO-67-NH 2 and MIL-100 (Fe) Surface modified metal organic framework for. The method according to claim 1,
The amine compound may be any one selected from the group consisting of triethylenediamine, triethylamine, quinuclidine, and pyridine-4-carboxylic acid, or a mixture thereof Characterized in that the surface modified metal organic framework for the removal of toxic gases. The method according to claim 1,
Wherein the surface-modified metal organic material is modified by a rotary evaporation method using a rotary evaporator or a vacuum evaporation method using a vacuum evaporator. The method according to claim 1,
Wherein the surface modified metal organic layer has a breakthrough time of 1000 min / g or more by weight of the toxic gas. The method according to claim 6,
Wherein the toxic gas is at least one selected from the group consisting of cyanogen chloride, dimethyl menthylphosphonate, ammonia, and sulfur dioxide. A product comprising a metal organic container according to any one of claims 1 to 6 for adsorbing and decomposing toxic gases. 9. The method of claim 8,
Characterized in that the product is a respirator, filter or protective material for respirators.

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