KR20210052864A - Metal-organic framework composite for decomposition volatile organic compounds and method of manufacturing same - Google Patents

Abstract

Disclosed are a metal-organic framework composite for decomposition of volatile organic compounds and a manufacturing method thereof. The metal-organic framework composite contains: metal-organic frameworks (MOFs) comprising pores; and metal nanoparticles supported on one or more surfaces selected from a group consisting of an outer surface of the metal-organic framework and a surface in contact with the pores of the metal-organic framework. The metal-organic framework composite of the present invention has the effect of adsorbing and completely decomposing VOCs at a low temperature.

Description

The metal-organic framework complex for decomposing volatile organic compounds and its manufacturing method TECHNICAL FIELD [METAL-ORGANIC FRAMEWORK COMPOSITE FOR DECOMPOSITION VOLATILE ORGANIC COMPOUNDS AND METHOD OF MANUFACTURING SAME}

The present invention relates to a metal-organic framework composite and a method for producing the same, and more particularly, to a metal-organic framework composite for decomposing volatile organic compounds and a method for producing the same.

As the public interest in living health and environmental health has increased, the government has established a “basic plan for indoor air quality management” and is managing air quality. In particular, in the case of volatile organic compounds (VOCs), it is known as a causative substance of ultrafine dust along with SOx and NOx, and VOCs themselves are harmful to humans, so a technology to remove them is required.

The existing activated carbon filter used as a VOC removal catalyst is inexpensive and has a high removal efficiency, but it is difficult to control the adsorption amount and requires periodic replacement.

In addition, in the VOC removal technology using the porous metal-organic framework (MOF), the porous metal-organic framework has been mainly used only as a gas storage or adsorbent. However, when VOCs are removed only by storage and adsorption, there is a problem in that VOCs are generated again when desorption.

An object of the present invention is to provide a metal-organic framework complex capable of adsorbing and completely decomposing VOCs at low temperatures.

According to an aspect of the present invention, a metal-organic framework (Metal-organic framework, MOFs) including pores; And metal nanoparticles supported on at least one surface selected from the group consisting of an outer surface of the metal-organic framework and a surface contacting the pores of the metal-organic framework. do.

In addition, the metal-organic framework may include a metal ion and an organic ligand coordinated to the metal ion.

In addition, the metal ions are zirconium (Zr), aluminum (Al), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), magnesium (Mg), It may contain one or more ions selected from the group consisting of chromium (Cr), indium (In), and gallium (Ga).

In addition, the organic ligand may include at least one selected from the group consisting of terephthalic acid, fumaric acid, oxalic acid, trimesic acid, and tribenzoic acid.

In addition, the metal-organic framework is UiO-66, UiO-67, UiO-68, MOF-5, MOF-177, MOF-801, MOF-804, MOF-805, MOF-806, MOF-808, MOF- 812, MOF-841, NU-100, NU-110, NU-1000, DUT-49, DUT-52, DUT-53, DUT-67, ZIF-8, IRMOF-20, CAU-10, MIL-100 and It may include one or more selected from the group consisting of MIL-101.

In addition, the metal nanoparticles are Pt, Au, Ag, Co, Cu, Fe, Ga, Hf, In, Ir, Mo, Mg, Ni, Nb, Pb, Pd, Rh, Re, Ru, Sb, Sn, Ta and It may include one or more selected from the group consisting of Te.

In addition, the size of the metal nanoparticles may be 0.5 to 20 nm.

In addition, the metal-organic framework composite is 100 parts by weight of the metal-organic framework; And 0.01 to 5 parts by weight of the metal nanoparticles.

In addition, the metal-organic framework complex may be used to decompose volatile organic compounds (VOCs).

In addition, the volatile organic compounds are benzene, toluene, ortho-xylene, meta-xylene, para-xylene, formaldehyde, acetaldehyde, acetylene, acetylene dichloride, acrolein, acrylonitrile, 1,3-butatiene, Butane, 1-butene, 2-butene, carbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, diethylamine, ethylene, n-hexane, isopropyl alcohol, methanol, methyl ethyl ketone, methylene chloride, MTBE ), propylene oxide, 1,1,1-trichloroethane, trichloroethylene, acetic acid, ethylbenzene, nitrobenzene, tetrachloroethylene, styrene, and at least one selected from the group consisting of isoprene.

According to another aspect of the present invention, there is provided a catalyst for decomposing volatile organic compounds including the metal-organic framework complex.

According to another aspect of the present invention, (a) dispersing the metal nanoparticles in a solvent to prepare a colloid including the metal nanoparticles; And (b) a metal-organic framework including pores by mixing and heat-treating the colloid and a metal-organic framework precursor, and the metal nanoparticles supported on a surface of the metal-organic framework in contact with the pores. A method of manufacturing a metal-organic framework composite comprising; preparing a metal-organic framework composite is provided.

In addition, the solvent may contain at least one selected from the group consisting of ethanol, methanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, acetone, dimethyl sulfoxide, and hexane. have.

In addition, the metal-organic framework precursors are zirconium (Zr), aluminum (Al), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), and magnesium. (Mg), chromium (Cr), indium (In), and may include a compound containing at least one selected from the group consisting of gallium (Ga).

In addition, the metal-organic framework precursor may include at least one selected from the group consisting of terephthalic acid, fumaric acid, oxalic acid, trimesic acid, and tribenzoic acid.

In addition, the heat treatment may be performed at a temperature of 50 to 200 °C.

According to another aspect of the present invention, (a) dispersing the metal nanoparticles in a solvent to prepare a colloid including the metal nanoparticles; (b) preparing a metal-organic framework comprising pores; And (c) mixing the colloid and the metal-organic framework and performing ultrasonic treatment to support the metal nanoparticles on the outer surface of the metal-organic framework to prepare a metal-organic framework composite; A method of manufacturing a metal-organic framework composite is provided.

The metal-organic framework composite of the present invention has the effect of adsorbing and completely decomposing VOCs at low temperatures.

1 is a schematic diagram showing the structure of UiO-66 manufactured according to Preparation Example 2.
2 is a schematic diagram showing the structure of MOF-801 manufactured according to Preparation Example 3.
3 is an HR-TEM image of Pt/UiO-66 prepared according to Example 1 and Pt⊂UiO-66 prepared according to Example 2. FIG.
4 is an HR-TEM image of Pt/MOF-801 prepared according to Example 3 and Pt⊂MOF-801 prepared according to Example 4. FIG.
5 is an XRD graph of Pt/UiO-66 prepared according to Example 1, Pt⊂UiO-66 prepared according to Example 2, and UiO-66 prepared according to Preparation Example 2. FIG.
6 is an XRD graph of Pt/MOF-801 prepared according to Example 3, Pt⊂MOF-801 prepared according to Example 4, and MOF-801 prepared according to Preparation Example 3. FIG.
7A is a graph showing toluene conversion (%) of Pt/UiO-66 prepared according to Example 1 according to temperature.
_{7B is a graph showing carbon dioxide (CO 2} ) voltage (mV) generated by decomposition of toluene by Pt/UiO-66 prepared according to Example 1. FIG.
_{7C is a graph showing a carbon dioxide (CO 2} ) area (mV·sec) generated by decomposition of toluene by Pt/UiO-66 prepared according to Example 1. FIG.
8A is a graph showing toluene conversion (%) of Pt⊂UiO-66 prepared according to Example 2 by temperature.
_{8B is a graph showing carbon dioxide (CO 2} ) voltage (mV) generated by decomposition of toluene by Pt⊂UiO-66 prepared according to Example 2. FIG.
_{8C is a graph showing the carbon dioxide (CO 2} ) area (mV·sec) generated by decomposition of toluene by Pt⊂UiO-66 prepared according to Example 2. FIG.
9A is a graph showing toluene conversion (%) by temperature of Pt/MOF-801 prepared according to Example 3. FIG.
_{9B is a graph showing carbon dioxide (CO 2} ) voltage (mV) generated by decomposition of toluene by Pt/MOF-801 prepared according to Example 3. FIG.
_{9C is a graph showing a carbon dioxide (CO 2} ) area (mV·sec) generated by decomposition of toluene by Pt/MOF-801 prepared according to Example 3. FIG.
10A is a graph showing toluene conversion (%) of Pt⊂MOF-801 prepared according to Example 4 by temperature.
_{10B is a graph showing carbon dioxide (CO 2} ) voltage (mV) generated by decomposition of toluene by Pt⊂MOF-801 prepared according to Example 4. FIG.
_{10C is a graph showing a carbon dioxide (CO 2} ) area (mV·sec) generated by decomposition of toluene by Pt⊂MOF-801 prepared according to Example 4. FIG.
11 is a graph showing the toluene conversion (%) of the metal-organic framework composites prepared according to Examples 1 to 4 at 120°C.
12 is a graph showing the toluene conversion (%) of the metal-organic framework composites prepared according to Examples 1 to 4 at 140°C.
13 is a graph showing toluene conversion (%) of the metal-organic framework composites prepared according to Examples 1 to 4 at 160°C.
14 is a graph showing toluene conversion (%) of the metal-organic framework composites prepared according to Examples 1 to 4 at 180°C.
15 is a graph showing toluene conversion (%) of the metal-organic framework composites prepared according to Examples 1 to 4 by temperature.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art may easily implement the present invention.

However, the following description is not intended to limit the present invention to a specific embodiment, and in describing the present invention, when it is determined that a detailed description of a related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted. .

The terms used herein are used only to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, elements, or combinations thereof described in the specification, but one or more other features It is to be understood that the possibility of the presence or addition of numbers, steps, actions, elements, or combinations thereof is not preliminarily excluded.

Hereinafter, the metal-organic framework composite of the present invention will be described.

The present invention comprises a metal-organic framework (Metal-organic framework, MOFs) including pores; And metal nanoparticles supported on at least one surface selected from the group consisting of an outer surface of the metal-organic framework and a surface contacting the pores of the metal-organic framework. do.

Metal-organic Framework

The metal-organic framework composite of the present invention includes a metal-organic framework, and the metal-organic framework may include pores.

The metal-organic framework may include a metal ion and an organic ligand coordinated to the metal ion.

The metal ions are zirconium (Zr), aluminum (Al), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), magnesium (Mg), chromium It may include one or more ions selected from the group consisting of (Cr), indium (In) and gallium (Ga), and preferably zirconium (Zr).

The organic ligand may include at least one selected from the group consisting of terephthalic acid, fumaric acid, oxalic acid, trimesic acid and tribenzoic acid, and preferably at least one selected from the group consisting of terephthalic acid and fumaric acid.

The metal-organic frameworks are UiO-66, UiO-67, UiO-68, MOF-5, MOF-177, MOF-801, MOF-804, MOF-805, MOF-806, MOF-808, MOF-812. , MOF-841, NU-100, NU-110, NU-1000, DUT-49, DUT-52, DUT-53, DUT-67, ZIF-8, IRMOF-20, CAU-10, MIL-100 and MIL It may include at least one selected from the group consisting of -101, and preferably at least one selected from the group consisting of UiO-66 and MOF-801.

1 and 2 are schematic diagrams showing structures of UiO-66 and MOF-801, respectively. In FIG. 1, 6.8 Å denotes the micro pore size in the tetrahedron cage, and 7.2 Å denotes the micro pore size in the octahedron cage. In FIG. 2, 5.4 Å denotes the micro pore size in the tetrahedron cage, and 7.0 Å denotes the micro pore size in the octahedron cage.

Metal nanoparticles

The metal-organic framework complex of the present invention includes metal nanoparticles, and the metal nanoparticles are selected from the group consisting of an outer surface of the metal-organic framework and a surface in contact with the pores of the metal-organic framework. It may be supported on more than one species surface.

The metal nanoparticles are Pt, Au, Ag, Co, Cu, Fe, Ga, Hf, In, Ir, Mo, Mg, Ni, Nb, Pb, Pd, Rh, Re, Ru, Sb, Sn, Ta and Te It may include at least one selected from the group consisting of, and preferably includes Pt.

The size of the metal nanoparticles may be 0.5 to 20 nm, preferably 1 to 5 nm. If the size of the metal nanoparticle is less than 0.5 nm, it is not preferable to have a size less than a single metal particle, and if it exceeds 20 nm, it is not preferable because it is difficult to have physicochemical properties as a nanoparticle.

The metal-organic framework composite includes 100 parts by weight of the metal-organic framework; And 0.01 to 5 parts by weight of the metal nanoparticles. If the amount of the metal nanoparticle is less than 0.01 parts by weight, it is not preferable because the active point is small and it is difficult to decompose the volatile organic compound, and if it exceeds 5 parts by weight, the efficiency of decomposition of the volatile organic compound per nanoparticle decreases, which is not preferable.

The metal-organic framework complex may be used to decompose volatile organic compounds (VOCs).

The volatile organic compounds are benzene, toluene, ortho-xylene, meta-xylene, para-xylene, formaldehyde, acetaldehyde, acetylene, acetylene dichloride, acrolein, acrylonitrile, 1, 3-butadiene, butane. , 1-butene, 2-butene, carbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, diethylamine, ethylene, n-hexane, isopropyl alcohol, methanol, methyl ethyl ketone, methylene chloride, MTBE , Propylene oxide, 1,1,1-trichloroethane, trichloroethylene, acetic acid, ethylbenzene, nitrobenzene, tetrachloroethylene, styrene and isoprene may contain at least one selected from the group consisting of, and preferably It may contain toluene.

In addition, the present invention provides a catalyst for decomposing volatile organic compounds including the metal-organic framework complex.

Hereinafter, a method of manufacturing the metal-organic framework composite of the present invention will be described.

First, a colloid containing the metal nanoparticles is prepared by dispersing the metal nanoparticles in a solvent (step a).

The solvent may include at least one selected from the group consisting of ethanol, methanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, acetone, dimethyl sulfoxide, and hexane. , Preferably it may contain ethanol.

The metal-organic framework precursors are zirconium (Zr), aluminum (Al), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), magnesium ( Mg), chromium (Cr), indium (In), and may include a compound containing at least one selected from the group consisting of gallium (Ga).

The metal-organic framework precursor may include at least one selected from the group consisting of terephthalic acid, fumaric acid, oxalic acid, trimesic acid, and tribenzoic acid.

Next, the colloid and metal-organic Framework Metal-organic containing pores by mixing and heat treatment of precursors Framework And the metal-organic Framework On the surface in contact with the pores Supported Metal-organic containing the metal nanoparticles Framework A large complex is prepared (step b).

The heat treatment may be performed at a temperature of 50 to 200 °C, and preferably may be performed at a temperature of 100 to 150 °C. If the heat treatment is less than 50°C, the activation energy for forming the metal-organic framework structure is insufficient, which is not preferable. If it exceeds 200°C, it is higher than the boiling point of the solvent to be used, which is not preferable.

Hereinafter, a method of manufacturing a metal-organic framework composite according to another embodiment of the present invention will be described.

First, a colloid containing the metal nanoparticles is prepared by dispersing the metal nanoparticles in a solvent (step a).

Next, metal-organic containing pores Framework To prepare (step b).

Finally, the colloid and the metal-organic Framework The metal-organic by mixing and sonicating Framework The metal nanoparticles on the outer surface Load it Metal-organic Framework Prepare the composite (step c).

The ultrasonic treatment may be performed for 30 to 100 minutes.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples. However, this is for illustrative purposes and is not intended to limit the scope of the present invention.

Preparation Example 1: Preparation of platinum (Pt) colloid

50 mL into a 20 mL ethylene glycol in a round bottom flask, 40 mg H ₂ PtCl ₆ 6H ₂ O and 222 mg _and the polyvinylpyrrolidone was added to the mixture (PVP, Mw. 55,000) was prepared. With stirring for at least 10 minutes, the mixture was emptied from the flask _{and refilled with N 2,} and the process was repeated two more times. Thereafter, the mixture was heated in an oil bath at 180° C. for 10 minutes, and the flask containing the mixture was lifted from the oil bath and cooled with air to prepare a colloid.

The colloid was divided into two 50 mL centrifuge tubes by 10 ml each, and acetone was added to each tube to precipitate Pt nanoparticles, followed by centrifugation at 8000 rpm for 5 minutes. The supernatant was discarded and 7.5 mL ethanol and 35 mL hexane were added. After washing three times, the two centrifuge tubes were combined into one, and Pt nanoparticles were dispersed in 15 ml ethanol to prepare 1 mg/mL Pt colloid.

Preparation Example 2: Preparation of UiO-66

In a 20 ml glass vial, _{33.4 mg of ZrCl 4} , 25 mg of terephthalic acid (BDC), 10 ml of DMF, and 0.7 ml of acetic acid were mixed to prepare a solution and placed in an oven at 120° C. for one day. The resulting powder was washed three times with DMF using a centrifuge (6,000 rpm for 10 minutes) and sonication, and then continuously immersed in methanol for three 24 hour cycles. Finally, UiO-66 was prepared by removing the solvent under vacuum for 12 hours at room temperature.

Preparation Example 3: Preparation of MOF-801

In a 20 ml glass vial, _{33.4 mg of ZrCl 4} , 18 mg of fumaric acid, 10 ml of DMF, and 1.2 ml of acetic acid were mixed to prepare a solution and placed in an oven at 120° C. for one day. The resulting powder was washed three times with DMF using a centrifuge (6,000 rpm for 10 minutes) and sonication, and then continuously immersed in methanol for three 24 hour cycles. Finally, MOF-801 was prepared by removing the solvent under vacuum for 12 hours at room temperature.

Example 1: Preparation of UiO-66 (Pt/UiO-66) in which Pt nanoparticles are supported on the outer surface

400 mg of UiO-66 prepared according to Preparation Example 2 was dispersed in ethanol, mixed with 0.05 ml of Pt colloid prepared according to Preparation Example 1, and sonicated for 1 hour. UiO-66 (Pt/UiO-66) in which Pt nanoparticles were supported on the outer surface was prepared by washing three times with ethanol using a centrifuge (8,000 rpm, 5 minutes).

Example 2: Pt nanoparticles on the surface in contact with the inner pores Supported UiO -66 (Pt⊂UiO-66) manufacturing

In a 20 ml glass vial, 0.05 mL of Pt colloid prepared according to Preparation Example 1, _{33.4 mg of ZrCl 4} , 25 mg of terephthalic acid (BDC), 10 ml of DMF, and 0.7 ml of acetic acid were mixed to prepare a solution and then in an oven at 120°C. Leave it for a day. The resulting powder was washed three times with DMF using a centrifuge (6,000 rpm for 10 minutes) and sonication, and then continuously immersed in methanol for three 24 hour cycles. Finally, the solvent was removed under vacuum at room temperature for 12 hours to prepare UiO-66 (Pt⊂UiO-66) carrying the Pt nanoparticles on the surface in contact with the inner pores.

Example 3: Preparation of MOF-801 (Pt/MOF-801) in which Pt nanoparticles are supported on the outer surface

Pt nanoparticles were applied to the outer surface in the same manner as in Example 1, except that MOF-801 prepared according to Preparation Example 3 was used instead of using Ui0-66 prepared according to Preparation Example 2 in Example 1. Supported MOF-801 (Pt/MOF-801) was prepared.

Example 4: Pt nanoparticles on the surface in contact with the inner pores Supported Manufactured MOF-801 (Pt⊂MOF-801)

In a 20 ml glass vial, 0.05 mL of Pt colloid prepared according to Preparation Example 1, _{33.4 mg of ZrCl 4} , 18 mg of fumaric acid, 10 ml of DMF, and 1.2 ml of acetic acid were mixed to prepare a solution, and in an oven at 120° C. for one day I put it. The resulting powder was washed three times with DMF using a centrifuge (6,000 rpm for 10 minutes) and sonication, and then continuously immersed in methanol for three 24 hour cycles. Finally, the solvent was removed under vacuum at room temperature for 12 hours to prepare MOF-801 (Pt⊂MOF-801) in which Pt nanoparticles were supported on the surface in contact with the inner pores.

[Test Example]

Test Example 1: HR-TEM (High-resolution transmission electron microscopy) analysis

3 is a HR-TEM image of Pt/UiO-66 prepared according to Example 1 and Pt⊂UiO-66 prepared according to Example 2, and FIG. 4 is a Pt/MOF-801 prepared according to Example 3 And HR-TEM images of Pt⊂MOF-801 prepared according to Example 4.

3 and 4, in Pt/UiO-66 and Pt/MOF-801, it can be seen that Pt nanoparticles are evenly distributed on the outer surface of the metal-organic framework, and Pt⊂UiO-66 and Pt⊂MOF- In 801, it was confirmed that the Pt nanoparticles were supported on the surface in contact with the internal pores of the metal-organic framework.

Test Example 2: XRD (X-ray diffraction) analysis

5 is an XRD graph of Pt/UiO-66 prepared according to Example 1, Pt⊂UiO-66 prepared according to Example 2, and UiO-66 prepared according to Preparation Example 2. FIG. Referring to FIG. 5, it was confirmed that the metal-organic framework structure was stably maintained even after the Pt nanoparticles were supported on the outer surface and the surface in contact with the inner pores.

6 is an XRD graph of Pt/MOF-801 prepared according to Example 3, Pt⊂MOF-801 prepared according to Example 4, and MOF-801 prepared according to Preparation Example 3. FIG. Referring to FIG. 6, it was confirmed that the metal-organic framework structure was stably maintained even after the Pt nanoparticles were supported on the outer surface and the surface in contact with the inner pores.

Test Example 3: Toluene decomposition performance evaluation

After drying the metal-organic framework composites prepared according to Examples 1 to 4 overnight in a vacuum oven at room temperature, a toluene reaction experiment was performed in a tube reactor. In order to reduce the differential pressure in the reactor, a powdery sample and quartz beads (50-250 μm) were mixed in a volume ratio of 1:1 to proceed with the reaction. The catalyst (metal-organic framework complex) volume was 0.7 mL, the flow rate was 200 mL/min, and the space velocity was 1700 h ^-1 . Toluene was used as a reaction gas with an oxygen balanced gas having a concentration of 5 ppm.

Toluene was analyzed using a FID detector (Flame ionization detector) in GC (Gas chromatography), and the _{generation of CO 2,} which is evidence of complete decomposition of toluene, was analyzed using a TCD detector (Thermal conductivity detector).

Toluene decomposition performance of Pt/UiO-66 prepared according to Example 1 by temperature is shown in FIGS. 7A to 7C. Referring to Figures 7a to 7c, the initial desorption was observed up to 160 ℃, and decomposition reaction of toluene was started at 180 ℃. More than 95% of toluene was decomposed at 220°C, and toluene was completely decomposed at 240°C.

Toluene decomposition performance of Pt⊂UiO-66 prepared according to Example 2 by temperature is shown in FIGS. 8A to 8C. Referring to FIGS. 8A to 8C, it can be observed that desorption is gradually exhibited over time at 80° C. and then saturated again. Toluene was decomposed from 160° C. and completely decomposed at 180° C.

Toluene decomposition performance by temperature of Pt/MOF-801 prepared according to Example 3 is shown in FIGS. 9A to 9C. 9A to 9C, the initial desorption was observed at 140° C. and decomposition was also observed. More than 99% of toluene was decomposed at 160°C and completely decomposed at 180°C.

The toluene decomposition performance of Pt⊂MOF-801 prepared according to Example 4 by temperature is shown in FIGS. 10A to 10C. Referring to FIGS. 10A to 10C, a toluene peak was not observed at room temperature, and initial desorption was observed at 120° C. and decomposition was also observed. More than 99% of toluene was decomposed at 160°C and completely decomposed at 180°C.

The toluene decomposition performance of the metal-organic framework composites prepared according to Examples 1 to 4 at 120° C., 140° C., 160° C., and 180° C. is shown in FIGS. 11 to 14, and the toluene conversion rate at each temperature is shown in FIG. 15. Indicated.

11 to 15, all of the metal-organic framework composites prepared according to Examples 1 to 4 showed a tendency of gradually increasing the conversion rate after toluene adsorbed at room temperature was desorbed at 80°C. The decomposition of Pt⊂MOF-801 started at the lowest temperature of 120℃, and the decomposition of Pt/MOF-801, Pt⊂UiO-66, and Pt/UiO-66 started at 140℃. Pt⊂MOF-801, Pt/MOF-801, Pt⊂UiO-66, and Pt/UiO-66 showed good catalytic activity in order, showing the best catalytic activity was Pt⊂MOF-801. In addition, the decomposition reaction of Pt⊂UiO-66, Pt/MOF-801, and Pt⊂MOF-801 was completed at 180°C, and the reaction of Pt/UiO-66 was completed at 240°C.

In the above, preferred embodiments of the present invention have been described, but those of ordinary skill in the relevant technical field can add, change, delete or add components within the scope not departing from the spirit of the present invention described in the claims. Various modifications and changes may be made to the present invention by addition or the like, and it will be said that this is also included within the scope of the present invention. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form. The scope of the present invention is indicated by the claims to be described later rather than the detailed description, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention. do.

Claims (17)

Metal-organic frameworks (MOFs) containing pores; And
Metal nanoparticles supported on at least one surface selected from the group consisting of an outer surface of the metal-organic framework and a surface contacting the pores of the metal-organic framework;
Metal-organic framework composite comprising. The method of claim 1,
The metal-organic framework complex, characterized in that the metal-organic framework comprises a metal ion and an organic ligand coordinated to the metal ion. The method of claim 2,
The metal ions are zirconium (Zr), aluminum (Al), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), magnesium (Mg), chromium (Cr), indium (In) and gallium (Ga), characterized in that it comprises at least one ion selected from the group consisting of a metal-organic framework complex. The method of claim 2,
The metal-organic framework complex, characterized in that the organic ligand contains at least one selected from the group consisting of terephthalic acid, fumaric acid, oxalic acid, trimesic acid and tribenzoic acid. The method of claim 1,
The metal-organic framework is UiO-66, UiO-67, UiO-68, MOF-5, MOF-177, MOF-801, MOF-804, MOF-805, MOF-806, MOF-808, MOF-812 , MOF-841, NU-100, NU-110, NU-1000, DUT-49, DUT-52, DUT-53, DUT-67, ZIF-8, IRMOF-20, CAU-10, MIL-100 and MIL Metal-organic framework composite, characterized in that it comprises at least one selected from the group consisting of -101. The method of claim 1,
The metal nanoparticles are Pt, Au, Ag, Co, Cu, Fe, Ga, Hf, In, Ir, Mo, Mg, Ni, Nb, Pb, Pd, Rh, Re, Ru, Sb, Sn, Ta and Te Metal-organic framework composite, characterized in that it comprises at least one selected from the group consisting of. The method of claim 1,
Metal-organic framework composite, characterized in that the size of the metal nanoparticles is 0.5 to 20 nm. The method of claim 1,
The metal-organic framework composite is 100 parts by weight of the metal-organic framework; And 0.01 to 5 parts by weight of the metal nanoparticles. The method of claim 1,
The metal-organic framework complex, characterized in that for use to decompose volatile organic compounds (Volatile organic compounds, VOCs), characterized in that the metal-organic framework complex. The method of claim 9,
The volatile organic compounds are benzene, toluene, ortho-xylene, meta-xylene, para-xylene, formaldehyde, acetaldehyde, acetylene, acetylene dichloride, acrolein, acrylonitrile, 1, 3-butadiene, butane. , 1-butene, 2-butene, carbon tetrachloride, chloroform, cyclohexane, 1,2-dichloroethane, diethylamine, ethylene, n-hexane, isopropyl alcohol, methanol, methyl ethyl ketone, methylene chloride, MTBE , Propylene oxide, 1,1,1-trichloroethane, trichloroethylene, acetic acid, ethylbenzene, nitrobenzene, tetrachloroethylene, styrene and isoprene- Organic framework complex. A catalyst for decomposing volatile organic compounds comprising the metal-organic framework complex of claim 1. (a) dispersing the metal nanoparticles in a solvent to prepare a colloid containing the metal nanoparticles; And
(b) a metal-organic framework including pores by mixing and heat-treating the colloid and a metal-organic framework precursor, and a metal including the metal nanoparticles supported on the surface of the metal-organic framework in contact with the pores -Preparing an organic framework composite;
Method for producing a metal-organic framework composite comprising. The method of claim 12,
The solvent comprises at least one selected from the group consisting of ethanol, methanol, propanol, iso-propanol, tert-butanol, n-butanol, methoxyethanol, ethoxyethanol, acetone, dimethyl sulfoxide, and hexane. Method for producing a metal-organic framework composite. The method of claim 12,
The metal-organic framework precursors are zirconium (Zr), aluminum (Al), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), manganese (Mn), magnesium ( Mg), chromium (Cr), indium (In) and gallium (Ga), characterized in that it comprises a compound containing at least one selected from the group consisting of a metal-organic framework composite manufacturing method. The method of claim 12,
The metal-organic framework precursor comprises at least one selected from the group consisting of terephthalic acid, fumaric acid, oxalic acid, trimesic acid, and tribenzoic acid. The method of claim 12,
The method of manufacturing a metal-organic framework composite, characterized in that the heat treatment is performed at a temperature of 50 to 200°C. (a) dispersing the metal nanoparticles in a solvent to prepare a colloid containing the metal nanoparticles;
(b) preparing a metal-organic framework comprising pores; And
(c) preparing a metal-organic framework composite by mixing the colloid and the metal-organic framework and performing ultrasonic treatment to support the metal nanoparticles on the outer surface of the metal-organic framework;
Method for producing a metal-organic framework composite comprising.

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