WO2022255596A1 - Surface of copper-based coordination polymer particles for capturing carbon dioxide and absorbing volatile organic compounds and preparation method therefor - Google Patents

Surface of copper-based coordination polymer particles for capturing carbon dioxide and absorbing volatile organic compounds and preparation method therefor Download PDF

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WO2022255596A1
WO2022255596A1 PCT/KR2022/002753 KR2022002753W WO2022255596A1 WO 2022255596 A1 WO2022255596 A1 WO 2022255596A1 KR 2022002753 W KR2022002753 W KR 2022002753W WO 2022255596 A1 WO2022255596 A1 WO 2022255596A1
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copper
cpp
adsorbent
polymer particles
carbon dioxide
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PCT/KR2022/002753
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French (fr)
Korean (ko)
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김승도
최성찬
조성갑
김의건
조성락
최용찬
강은실
윤소영
레티감반
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한림대학교 산학협력단
주식회사 나노이노텍
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Publication of WO2022255596A1 publication Critical patent/WO2022255596A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28028—Particles immobilised within fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/14—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/14—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification
    • F24F3/1411—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification by absorbing or adsorbing water, e.g. using an hygroscopic desiccant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a surface of copper-based coordination polymer particles for capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same, and in particular, to a novel adsorbent comprising a surface of copper-based coordination polymer particles coated on a nonwoven fabric surface, and It relates to a manufacturing method thereof.
  • non-woven fibers are widely used as commercial air filtration substrates because the curved channels formed by randomly stacked fibers are advantageous for increasing filtration, but have limitations as a single material, and copper-based coordinating polymer particles Although it can be used as an adsorbent material, it has a problem in that it is difficult to apply to a gas containing pollutants because it is in the form of a powder.
  • An object of the present invention is to provide a copper-based coordinated polymer particle surface for stably capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same.
  • a gas adsorbent including nonwoven fibers coated with copper-based coordination polymer particles is provided.
  • the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
  • the ligand may be any one or more selected from those represented by the following formulas 1 to 2:
  • R 1 is -F, -Cl, -Br, -I, -S - , -O - , -NO 2 , -CN, -SO 3 - -COO - or -COCl - ;
  • R 2 to R 4 are each independently -H, -CH 3 or -C 2 H 5 ;
  • p is 0 to 3;
  • the nonwoven fabric may have a melting point of 115 ° C. or higher.
  • the nonwoven fabric fiber may be a condensed polymer material.
  • the gas may include at least one selected from volatile organic compounds and carbon dioxide.
  • immersing non-woven fibers in a solution containing copper-based coordination polymer particles processing at 115° C. to 140° C. for 4 to 12 hours; And it is possible to provide a method for preparing a gas adsorbent, including; washing and drying.
  • the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
  • the gas may include at least one selected from volatile organic compounds and carbon dioxide.
  • an adsorbent prepared by the method of the present invention may be provided.
  • an air purifier including the adsorbent of the present invention may be provided.
  • the present invention can effectively remove carbon dioxide and volatile organic compounds by providing a copper-based coordination polymer particle surface for capturing carbon dioxide and absorbing volatile organic compounds.
  • Figure 1 shows the synthesis of a nonwoven fiber (NWF) surface decorated with copper-based coordination polymer particles (Cu-CPP) by an in situ growth method.
  • NWF nonwoven fiber
  • Cu-CPP copper-based coordination polymer particles
  • SEM 2 is a scanning electron microscope (SEM) confirming the surface morphology of the nonwoven fabric fiber before the Cu-CPP coating.
  • 3 is a scanning electron microscope to confirm the surface morphology of nonwoven fibers after Cu-CPP coating.
  • FIG. 7 is a schematic diagram showing equipment for confirming p-xylene adsorption efficiency of Cu-CPP/NWF.
  • FIG. 10 is a schematic diagram showing the p-xylene adsorption mechanism of Cu-CPP.
  • FIG. 12 is a schematic diagram showing the carbon dioxide adsorption mechanism of Cu-CPP.
  • An object of the present invention is to provide a copper-based coordinated polymer particle surface for stably capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same.
  • Cu-based coordination polymer particles refers to a compound composed of copper ions or clusters coordinated to organic ligands, and includes copper ions acting as Lewis acids and It can be used as a heterogeneous catalyst showing different substrate selectivity and efficiency depending on the various structures formed between organic compounds acting as Lewis bases.
  • VOCs Volatile Organic Compounds
  • a gas adsorbent including nonwoven fibers coated with copper-based coordination polymer particles is provided.
  • the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
  • the ligand may be at least one selected from those represented by Formulas 1 and 2 below:
  • R 1 may be included without limitation as long as it is an element or ion capable of functioning as a Lewis base, but is preferably -F, -Cl, -Br, -I, -S - , -O - , -NO 2 , -CN, -SO 3 - -COO - or -COCl - ; R 2 to R 4 are each independently -H, -CH 3 or -C 2 H 5 ; p may be 0 to 3.
  • the copper-based coordinated polymer particles including Chemical Formulas 1 and 2 are connected to the center of the node, and the cation- ⁇ interaction between the aromatic of the volatile organic compound and the copper metal and the ⁇ - between the aromatic of the volatile organic compound and the Chemical Formulas 1 to 2 A geometric structure capable of adsorbing the volatile organic compound may be provided through the ⁇ interaction.
  • the copper-based coordination polymer particles including Formulas 1 to 2 provide an unsaturated copper ion center through a paddle wheel structure to induce a large quadrupole moment of carbon dioxide through an electrostatic interaction with carbon dioxide, and selectively release carbon dioxide. It is possible to form a cavity of a size that can be captured by
  • the ligand may be represented by the following Chemical Formulas 3 to 5:
  • R 5 is -H or -CH 3 .
  • the ligand is trimesic acid (benzene-1,3,5-tricarboxylic acid; Trimesic acid), 1,3,5-tris (bromomethyl) -2,4,6-trimethylbenzene (1, 3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene; C 12 H 15 Br 3 ) and 1,3,5-tris(4-carboxyphenyl)benzene (1,3,5-Tris(4- It may be one or more selected from carboxyphenyl)benzene; H 3 BTB).
  • the nonwoven fabric may have a melting point of 115° C. or higher.
  • the melting point of the nonwoven fiber is less than 115° C., denaturation may occur while the copper-based coordination polymer particles are coated on the surface of the nonwoven fabric.
  • the nonwoven fabric fiber may be a condensed polymer material, preferably at least one selected from polyester and polyamide.
  • the condensation polymer prepared by condensation polymerization of monomers has a higher heat resistance effect than the polymer prepared by addition polymerization of monomers, and can stably provide a surface structure of the adsorbent.
  • the gas may include at least one selected from volatile organic compounds and carbon dioxide, and preferably, the volatile organic compounds may be aromatic compounds.
  • the volatile organic compound may be any one or more selected from benzene, ethylene glycol, formaldehyde, methylene chloride, tetrachloroethylene, toluene, xylene and 1,3-butadiene, more preferably p-xylene (p-Xylene).
  • the volatile organic compound and carbon dioxide can be captured or absorbed on the surface of the copper-based coordination polymer particle of the present invention to improve air quality.
  • immersing the non-woven fabric fibers in a solution containing copper-based coordination polymer particles; processing at 115° C. to 140° C. for 4 to 12 hours; And washing and drying; containing, an adsorbent manufacturing method may be provided.
  • the treatment temperature when the treatment temperature is less than 115 ° C., the reaction may not sufficiently occur, and when the treatment temperature is higher than 140 ° C., the surface area may not be maximized because the copper-based coordination polymer particles are not evenly distributed.
  • the treatment time is less than 4 hours, the reaction may not sufficiently occur, and if the treatment time is more than 12 hours, the surface area of the copper-based coordination polymer particles may not be maximized.
  • the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
  • the copper-based coordination polymer particle may be any one selected from Chemical Formulas 1 to 2 described above, preferably any one selected from Chemical Formulas 3 to 5 described above.
  • the nonwoven fabric may have a melting point of 115° C. or higher.
  • the melting point of the nonwoven fabric is less than 115° C., modification may occur during the treatment so that the copper-based coordination polymer particles are coated on the surface of the nonwoven fabric.
  • the gas may include at least one selected from volatile organic compounds and carbon dioxide.
  • an adsorbent prepared by the method of the present invention may be provided.
  • a filtration membrane, a filter, an air purifier, an air conditioner, an air conditioner, and the like including the adsorbent of the present invention may be provided.
  • the surface of nonwoven fibers (NWF) decorated with copper-based coordinating polymer particles (Cu-CPP) was synthesized by an in situ growth method. Specifically, 2.18 g of Cu(NO 3 ) 2 .3H 2 O was dissolved in 60 mL of an aqueous solution, and then 60 mL of an ethanol solution containing 1.05 g of trimesic acid as an organic ligand was poured. The mixed solution was vortexed, shaken, and sonicated for 4 minutes.
  • NWF nonwoven fabric
  • Cu-CPP copper-based coordination polymer particles
  • Cu-CPP copper-based coordination polymer particles
  • Cu-CPP copper-based coordination polymer particles
  • the normal material growth method of Preparation Example 1 was used, but 1,3,5-tris (bromomethyl) -2,4, Cu-CPP was prepared using 6-trimethylbenzene (1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene; C 12 H 15 Br 3 ).
  • Cu-CPP copper-based coordination polymer particle
  • the normal material growth method of Preparation Example 1 was used, but 1,3,5-tris (4-carboxyphenyl) benzene (1, Cu-CPP was prepared using 3,5-Tris(4-carboxyphenyl)benzene; H 3 BTB).
  • Cu-CPP copper-based coordination polymer particles
  • the normal material growth method of Preparation Example 1 was used, but 2,5-dihydroxyterephthalic acid (2,5-dihydroxyterephthalic acid) was used as an organic ligand. acid; dhtp) was used to prepare Cu-CPP.
  • Cu-CPP copper-based coordination polymer particles
  • Comparative Example 8 the normal material growth method of Preparation Example 1 was used, but Cu-CPP was prepared using fumaric acid as an organic ligand.
  • Cu-CPP copper-based coordination polymer particles
  • Comparative Example 9 the normal material growth method of Preparation Example 1 was used, but Cu-CPP was prepared using propanedioic acid as an organic ligand.
  • the BET surface area (SBET) of Preparation Examples 1 to 5 is 1,200 m 2 /g or more and the pore volume (VBJH) is 0.4 cm 2 /g or more, which is comparable to Comparative Examples 1 to 9 and This is a significantly higher value than the BET surface area and pore volume of activated carbon, and the average pore diameter of Preparation Examples 1 to 5 is also 12 ⁇ or more, which is significantly higher than that of Comparative Examples 1 to 9.
  • Use of trimesic acid or dhtp organic ligand After manufacturing Cu-CPP, the effect of excellent surface properties was confirmed in the case of the copper surface grown on polyester, polyamide, polycarbonate or polyphenylene oxide nonwoven fiber material at 120 ° C. for 6 hours.
  • Example 1 the surface morphology of the nonwoven fabric (NWF) before the Cu-CPP coating was confirmed with a scanning electron microscope (SEM) and shown in FIG. 2, and the surface morphology of the nonwoven fabric (NWF) after the Cu-CPP coating The surface morphology was confirmed with a scanning electron microscope (SEM) and shown in FIG. 3 .
  • the nonwoven fabric before Cu-CPP coating showed a clean and smooth surface and a wavy channel
  • the result showed Cu- The appearance of CPP microcrystals was clearly detected.
  • the Cu-CPP crystals densely covered the non-woven fabric (NWF) and each had a diameter of about 12 ⁇ m using an octahedral topology.
  • EDS energy-dispersive spectrum
  • the peaks of carbon and oxygen, which are the main elements forming nonwoven fabric fibers, are displayed, and the peak of copper is also displayed, indicating that all elements constituting the Cu-CPP/NWF are uniformly distributed over the entire surface of the filter. Bar, it was confirmed that Cu-CPP was successfully grown on nonwoven fabric fibers.
  • the nitrogen gas absorption ability according to the change of the BET surface area was evaluated. Specifically, nitrogen gas absorption isotherms of Cu-CPP/NWF (or Cu-CPP microcrystals) according to Preparation Example 1 and Cu-CPP/NWF according to Comparative Example 3 and non-woven fabric fibers without copper coating were measured, and FIG. 6 shown in
  • the amount of p-xylene absorbed by using nonwoven fabric (NWF) was measured by GC/MS and shown in FIGS. 8 and 9 .
  • the nonwoven fabric (NWF) used as a control has no absorption capacity, whereas the Cu-CPP/NWF filter absorbs up to 100% p-xylene for 350 minutes, reducing carcinogenic volatility. It was confirmed that organic compounds can be utilized in high-efficiency and eco-friendly processes for decontamination.
  • Cu-CPP adsorbs p-xylene. Since Cu-CPP composed of copper cations can be adsorbed through the cation- ⁇ interaction between the aromatics of p-xylene and the metal as the connecting center of the node, the Cu-CPP of the present invention has an adsorption effect of volatile organic compound contaminants. It was possible to confirm that In addition, Cu-CPP has 1,3,5-benzene tricarboxylic acid as an organic linker, which was effective for adsorption due to the ⁇ - ⁇ interaction between the phenyl ring of p-xylene and the Cu-CPP structure. Moreover, the large cavities and rich gas adsorption sites of Cu-CPP together with the very high surface area provided a positive contribution to the adsorption of contaminants.
  • the carbon dioxide gas absorbing ability according to the change of the BET surface area was evaluated. Specifically, Cu-CPP/NWF (or Cu-CPP microcrystals) according to Preparation Example 1 and Cu-CPP/NWF and non-copper coated NWF according to Comparative Example 3 respectively absorb carbon dioxide at 0 bar to 1 bar. The ability to do was confirmed and shown in Figure 11.
  • the pure nonwoven fabric had no carbon dioxide adsorption activity, whereas the Cu-CPP microcrystals showed excellent adsorption performance with a relatively high adsorption capacity of 34.47 cm 3 /g.
  • Cu-CPP microcrystals are in powder form, they can clog pipes and cause large gas resistance in practical applications, so it is preferable to use Cu-CPP/NWF in dynamic processes and practical applications.
  • Comparative Example 3 it had an adsorption capacity of 19.81 cm 3 /g, and it was confirmed that it had a higher carbon dioxide adsorption capacity than pure nonwoven fabric fibers.
  • FIG. 12 is a schematic diagram showing the carbon dioxide adsorption mechanism of Cu-CPP.
  • the carbon dioxide adsorption mechanism was confirmed by the high porosity, large specific surface area and abundant open metal sites of the Cu-CPP deposited on the fibers.
  • the two major adsorption sites contributing to the carbon dioxide adsorption mechanism of Cu-CPP are open metal sites and small cage window sites.
  • the site was, firstly, that open metal ions could expose equally unsaturated copper ion centers through a paddlewheel structure, which led to the polarization of carbon dioxide through electrostatic interactions and to make carbon dioxide have a large quadrupole moment. induced, contributing to having the strongest binding site.
  • An object of the present invention is to provide a copper-based coordinated polymer particle surface for stably capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same.

Abstract

The present invention relates to a surface of copper-based coordination polymer particles for capturing carbon dioxide and absorbing volatile organic compounds and a preparation method therefor and, specifically, to a novel adsorbent comprising a surface of copper-based coordination polymer particles coated on a surface of a non-woven fabric and a manufacturing method for the adsorbent.

Description

이산화탄소 포집 및 휘발성 유기 화합물 흡수를 위한 구리 기반 배위 고분자 입자 표면 및 이의 제조방법 Surface of copper-based coordinating polymer particles for capturing carbon dioxide and absorbing volatile organic compounds and method for preparing the same
본 발명은 이산화탄소를 포집하고 및 휘발성 유기 화합물을 흡수하기 위한 구리 기반 배위 고분자 입자 표면 및 이의 제조방법에 관한 것으로, 상세하게는 부직포 표면에 코팅된 구리 기반 배위 고분자 입자 표면을 포함하는 신규한 흡착제 및 이의 제조방법에 관한 것이다. The present invention relates to a surface of copper-based coordination polymer particles for capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same, and in particular, to a novel adsorbent comprising a surface of copper-based coordination polymer particles coated on a nonwoven fabric surface, and It relates to a manufacturing method thereof.
환경 오염으로 인하여 공기질에 대한 관심이 높아지고 있지만, 현재 이산화탄소와 휘발성 유기 화합물(Volatile Organic Compounds; VOCs)를 효과적으로 처리할 수 있는 기능을 가진 필터 또는 장치가 부족하여, 상기 기능을 가진 청정기 개발이 절실하다. Although interest in air quality is increasing due to environmental pollution, there is currently a lack of filters or devices with functions that can effectively treat carbon dioxide and volatile organic compounds (VOCs), so it is urgent to develop a purifier with these functions. .
이를 해결하기 위한 소재 중, 부직포 섬유는 무작위로 쌓인 섬유에 의해 형성된 굴곡 진 채널이 여과 증가에 유리하기 때문에 상업적인 공기 여과 기질로 널리 사용되나, 단일 소재인 한계를 가지고, 구리 기반의 배위 고분자 입자는 흡착제 재료로 사용될 수 있으나, 분말 형태인 관계로 오염 물질이 포함된 기체에 적용하기 어려운 문제를 가지고 있다.Among the materials to solve this problem, non-woven fibers are widely used as commercial air filtration substrates because the curved channels formed by randomly stacked fibers are advantageous for increasing filtration, but have limitations as a single material, and copper-based coordinating polymer particles Although it can be used as an adsorbent material, it has a problem in that it is difficult to apply to a gas containing pollutants because it is in the form of a powder.
본 발명은 안정적으로 이산화탄소를 포집하고 및 휘발성 유기 화합물을 흡수하기 위한 구리 기반 배위 고분자 입자 표면 및 이의 제조방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a copper-based coordinated polymer particle surface for stably capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same.
본 발명이 해결하고자 하는 과제들은 이상에서 언급된 과제로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다. 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 description below.
상기와 같은 목적을 달성하기 위하여, 본 발명의 일 실시예에 따르면 구리 기반 배위 고분자 입자가 표면에 코팅된 부직포 섬유를 포함하는 기체 흡착제가 제공된다. In order to achieve the above object, according to an embodiment of the present invention, a gas adsorbent including nonwoven fibers coated with copper-based coordination polymer particles is provided.
또한 본 발명에서, 상기 구리 기반 배위 고분자 입자는 1 또는 4개의 방향족 고리를 갖는 리간드를 포함하는 것일 수 있다.Also, in the present invention, the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
또한 본 발명에서, 상기 리간드는 하기 화학식 1 내지 2로 표시되는 것에서 선택된 어느 하나 이상일 수 있다:In addition, in the present invention, the ligand may be any one or more selected from those represented by the following formulas 1 to 2:
[화학식 1][Formula 1]
Figure PCTKR2022002753-appb-img-000001
Figure PCTKR2022002753-appb-img-000001
[화학식 2][Formula 2]
Figure PCTKR2022002753-appb-img-000002
Figure PCTKR2022002753-appb-img-000002
상기 화학식 1 내지 2에서, R1은 -F, -Cl, -Br, -I, -S-, -O-, -NO2, -CN, -SO3 - -COO- 또는 -COCl-이고; R2 내지 R4는 서로 독립적으로 -H, -CH3 또는 -C2H5이고; p는 0 내지 3이다. In Formulas 1 and 2, R 1 is -F, -Cl, -Br, -I, -S - , -O - , -NO 2 , -CN, -SO 3 - -COO - or -COCl - ; R 2 to R 4 are each independently -H, -CH 3 or -C 2 H 5 ; p is 0 to 3;
또한 본 발명에서, 상기 부직포 섬유는 녹는점이 115℃ 이상인 것일 수 있다.In addition, in the present invention, the nonwoven fabric may have a melting point of 115 ° C. or higher.
또한 본 발명에서, 상기 부직포 섬유는 축합폴리머 소재일 수 있다.Also, in the present invention, the nonwoven fabric fiber may be a condensed polymer material.
또한 본 발명에서, 상기 기체는 휘발성 유기 화합물 및 이산화탄소에서 선택된 어느 하나 이상을 포함하는 것일 수 있다.Also, in the present invention, the gas may include at least one selected from volatile organic compounds and carbon dioxide.
본 발명의 다른 일 실시예에 따르면, 구리 기반 배위 고분자 입자를 포함하는 용액에 부직포 섬유를 담그는 단계; 115℃ 내지 140℃에서 4시간 내지 12시간동안 처리하는 단계; 및 세척 및 건조하는 단계;를 포함하는, 기체 흡착제 제조방법을 제공할 수 있다.According to another embodiment of the present invention, immersing non-woven fibers in a solution containing copper-based coordination polymer particles; processing at 115° C. to 140° C. for 4 to 12 hours; And it is possible to provide a method for preparing a gas adsorbent, including; washing and drying.
또한 본 발명에서, 상기 구리 기반 배위 고분자 입자는 1 또는 4개의 방향족 고리를 갖는 리간드를 포함하는 것일 수 있다.Also, in the present invention, the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
또한 본 발명에서, 상기 기체는 휘발성 유기 화합물 및 이산화탄소에서 선택된 어느 하나 이상을 포함하는 것일 수 있다.Also, in the present invention, the gas may include at least one selected from volatile organic compounds and carbon dioxide.
본 발명의 또 다른 일 실시예에 따르면, 본 발명의 방법에 의해 제조된, 흡착제를 제공하는 것일 수 있다.According to another embodiment of the present invention, an adsorbent prepared by the method of the present invention may be provided.
본 발명의 또 다른 일 실시예에 따르면, 본 발명의 흡착제를 포함하는 공기청정기를 제공하는 것일 수 있다.According to another embodiment of the present invention, an air purifier including the adsorbent of the present invention may be provided.
본 발명의 또 다른 일 실시예에 따르면, 본 발명의 흡착제를 포함하는 공기조화기를 제공하는 것일 수 있다.According to another embodiment of the present invention, it may be to provide an air conditioner including the adsorbent of the present invention.
본 발명은 이산화탄소를 포집하고 및 휘발성 유기 화합물을 흡수하기 위한 구리 기반 배위 고분자 입자 표면을 제공하여 효과적으로 이산화탄소 및 휘발성 유기 화합물을 제거할 수 있다.The present invention can effectively remove carbon dioxide and volatile organic compounds by providing a copper-based coordination polymer particle surface for capturing carbon dioxide and absorbing volatile organic compounds.
본 발명의 효과들은 이상에서 언급된 효과로 제한되지 않으며, 언급되지 않은 또 다른 효과들은 아래의 기재로부터 통상의 기술자에게 명확하게 이해될 수 있을 것이다.The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description below.
도 1은 구리 기반 배위 고분자 입자(Cu-CPP)로 데코레이트된 부직포 섬유(NWF) 표면을 정상 소재 성장 방법(in situ growth method)에 의해 합성되는 것을 나타낸 것이다. Figure 1 shows the synthesis of a nonwoven fiber (NWF) surface decorated with copper-based coordination polymer particles (Cu-CPP) by an in situ growth method.
도 2는 Cu-CPP 코팅을 하기 전 부직포 섬유의 표면 형태를 주사 전자 현미경(SEM)으로 확인한 것이다.2 is a scanning electron microscope (SEM) confirming the surface morphology of the nonwoven fabric fiber before the Cu-CPP coating.
도 3은 Cu-CPP 코팅을 한 후 부직포 섬유의 표면 형태를 주사 전자 현미경으로 확인한 것이다.3 is a scanning electron microscope to confirm the surface morphology of nonwoven fibers after Cu-CPP coating.
도 4는 Cu-CPP 코팅을 한 후 Cu-CPP/NWF의 에너지 분산 스펙트럼 매핑을 실시한 결과를 나타낸 것이다.4 shows the results of energy dispersive spectrum mapping of Cu-CPP/NWF after Cu-CPP coating.
도 5는 Cu-CPP 코팅을 한 후 Cu-CPP/NWF 구조의 결정도를 추가로 평가하고 부직포 섬유에서 Cu-CPP의 존재를 확인하기 위하여, X-선 회절(XRD) 분석을 실시한 결과를 나타낸 것이다.5 shows the results of X-ray diffraction (XRD) analysis to further evaluate the crystallinity of the Cu-CPP / NWF structure after Cu-CPP coating and to confirm the presence of Cu-CPP in nonwoven fibers .
도 6은 BET 표면적의 변화에 따른 질소 기체 흡수 능력을 평가를 실시한 결과를 나타낸 것이다.6 shows the results of evaluating the nitrogen gas absorbing ability according to the change in the BET surface area.
도 7은 Cu-CPP/NWF의 p-자일렌 흡착 효율을 확인하기 위한 장비를 나타낸 모식도이다.7 is a schematic diagram showing equipment for confirming p-xylene adsorption efficiency of Cu-CPP/NWF.
도 8은 Cu-CPP/NWF의 p-자일렌 흡착 효율을 확인한 결과를 나타낸 것이다.8 shows the result of confirming the p-xylene adsorption efficiency of Cu-CPP/NWF.
도 9는 Cu-CPP/NWF의 p-자일렌 흡착 효율을 확인한 결과를 나타낸 것이다.9 shows the result of confirming the p-xylene adsorption efficiency of Cu-CPP/NWF.
도 10은 Cu-CPP의 p-자일렌 흡착 메커니즘을 모식도로 나타낸 것이다.10 is a schematic diagram showing the p-xylene adsorption mechanism of Cu-CPP.
도 11은 BET 표면적의 변화에 따른 이산화탄소 기체 흡수 능력을 평가한 결과를 나타낸 것이다.11 shows the result of evaluating the carbon dioxide gas absorbing ability according to the change in the BET surface area.
도 12는 Cu-CPP의 이산화탄소 흡착 메커니즘을 모식도로 나타낸 것이다.12 is a schematic diagram showing the carbon dioxide adsorption mechanism of Cu-CPP.
본 발명은 안정적으로 이산화탄소를 포집하고 및 휘발성 유기 화합물을 흡수하기 위한 구리 기반 배위 고분자 입자 표면 및 이의 제조방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a copper-based coordinated polymer particle surface for stably capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same.
이하, 본 발명에 대하여 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 특허청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서, 본 명세서에 기재된 실시예에 기재된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Hereinafter, the present invention will be described in detail. Prior to this, terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor appropriately uses the concept of terms in order to describe his/her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical spirit of the present invention based on the principle that it can be defined in the following way. Therefore, the configuration described in the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent all of the technical ideas of the present invention, so various equivalents and equivalents that can replace them at the time of this application It should be understood that variations may exist.
본 발명에서, 용어 “구리 기반 배위 고분자 입자(Cu-based coordination polymer particles; Cu-CPP)”는 유기 리간드에 배위된 구리 이온 또는 클러스터로 구성된 화합물을 총칭하는 것으로, 루이스 산으로 작용하는 구리 이온과 루이스 염기로 작용하는 유기 화합물 간 형성하는 다양한 구조에 따라 상이한 기질 선택성 및 효율성을 보이는 이종 촉매로 사용될 수 있다. In the present invention, the term “Cu-based coordination polymer particles (Cu-CPP)” refers to a compound composed of copper ions or clusters coordinated to organic ligands, and includes copper ions acting as Lewis acids and It can be used as a heterogeneous catalyst showing different substrate selectivity and efficiency depending on the various structures formed between organic compounds acting as Lewis bases.
본 발명에서, 용어 “휘발성 유기 화합물(Volatile Organic Compounds; VOCs)”은 증기압이 높아 대기 중으로 쉽게 증발되는 액체 또는 기체상 유기화합물의 총칭으로, 광화학 스모그를 유발할 뿐 아니라 발암성 물질이고, 지구온난화의 원인 물질이므로 국가마다 배출을 줄이기 위해 정책적으로 관리하고 있는 것이다.In the present invention, the term “Volatile Organic Compounds (VOCs)” is a general term for liquid or gaseous organic compounds that are easily evaporated into the atmosphere due to their high vapor pressure, which not only cause photochemical smog but also are carcinogenic and contribute to global warming. Since it is a causative substance, each country manages it as a policy to reduce emissions.
본 발명의 일 실시예에 따라, 구리 기반 배위 고분자 입자가 표면에 코팅된 부직포 섬유를 포함하는 기체 흡착제가 제공된다.According to one embodiment of the present invention, a gas adsorbent including nonwoven fibers coated with copper-based coordination polymer particles is provided.
본 발명에서, 상기 구리 기반 배위 고분자 입자는 1 또는 4개의 방향족 고리를 갖는 리간드를 포함하는 것일 수 있다.In the present invention, the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
본 발명에서, 상기 리간드는 하기 화학식 1 내지 2로 표시되는 것에서 선택된 어느 하나 이상일 수 있다:In the present invention, the ligand may be at least one selected from those represented by Formulas 1 and 2 below:
[화학식 1][Formula 1]
Figure PCTKR2022002753-appb-img-000003
Figure PCTKR2022002753-appb-img-000003
[화학식 2][Formula 2]
Figure PCTKR2022002753-appb-img-000004
Figure PCTKR2022002753-appb-img-000004
단, 상기 화학식 1 내지 2에서, R1은 루이스 염기로 기능할 수 있는 원소 또는 이온이면 제한없이 포함될 수 있으나, 바람직하게는 -F, -Cl, -Br, -I, -S-, -O- , -NO2, -CN, -SO3 - -COO- 또는 -COCl-이고; R2 내지 R4는 서로 독립적으로 -H, -CH3 또는 -C2H5이고; p는 0 내지 3일 수 있다. 상기 화학식 1 내지 2를 포함하는 구리 기반 배위 고분자 입자는 노드의 연결 중심으로서 휘발성 유기 화합물의 방향족과 구리 금속 사이의 양이온-π 상호 작용 및 휘발성 유기 화합물의 방향족과 상기 화학식 1 내지 2 사이의 π-π 상호 작용을 통하여 상기 휘발성 유기 화합물을 흡착할 수 있는 기하학적인 구조를 제공할 수 있다. 또한, 상기 화학식 1 내지 2를 포함하는 구리 기반 배위 고분자 입자는 패들휠 구조를 통하여, 불포화된 구리 이온 중심을 제공하여 이산화탄소와 정전기 상호 작용을 통해 이산화탄소의 사중극성 모멘트를 크게 유도하고, 이산화탄소를 선택적으로 포획할 수 있는 크기의 공동을 형성할 수 있다.However, in Formulas 1 and 2, R 1 may be included without limitation as long as it is an element or ion capable of functioning as a Lewis base, but is preferably -F, -Cl, -Br, -I, -S - , -O - , -NO 2 , -CN, -SO 3 - -COO - or -COCl - ; R 2 to R 4 are each independently -H, -CH 3 or -C 2 H 5 ; p may be 0 to 3. The copper-based coordinated polymer particles including Chemical Formulas 1 and 2 are connected to the center of the node, and the cation-π interaction between the aromatic of the volatile organic compound and the copper metal and the π- between the aromatic of the volatile organic compound and the Chemical Formulas 1 to 2 A geometric structure capable of adsorbing the volatile organic compound may be provided through the π interaction. In addition, the copper-based coordination polymer particles including Formulas 1 to 2 provide an unsaturated copper ion center through a paddle wheel structure to induce a large quadrupole moment of carbon dioxide through an electrostatic interaction with carbon dioxide, and selectively release carbon dioxide. It is possible to form a cavity of a size that can be captured by
본 발명에서, 상기 리간드는 하기 화학식 3 내지 5로 표시되는 것일 수 있다:In the present invention, the ligand may be represented by the following Chemical Formulas 3 to 5:
[화학식 3][Formula 3]
Figure PCTKR2022002753-appb-img-000005
Figure PCTKR2022002753-appb-img-000005
[화학식 4][Formula 4]
Figure PCTKR2022002753-appb-img-000006
Figure PCTKR2022002753-appb-img-000006
[화학식 5][Formula 5]
Figure PCTKR2022002753-appb-img-000007
Figure PCTKR2022002753-appb-img-000007
단, 상기 화학식 3 내지 5에서, R5는 -H 또는 -CH3이다.However, in Chemical Formulas 3 to 5, R 5 is -H or -CH 3 .
본 발명에서, 상기 리간드는 트라이메스산(benzene-1,3,5-tricarboxylic acid; Trimesic acid), 1,3,5-트리스(브로모메틸)-2,4,6-트리메틸벤젠(1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene; C12H15Br3) 및 1,3,5-트리스(4-카르복시페닐)벤젠(1,3,5-Tris(4-carboxyphenyl)benzene; H3BTB)에서 선택된 어느 하나 이상인 것일 수 있다. In the present invention, the ligand is trimesic acid (benzene-1,3,5-tricarboxylic acid; Trimesic acid), 1,3,5-tris (bromomethyl) -2,4,6-trimethylbenzene (1, 3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene; C 12 H 15 Br 3 ) and 1,3,5-tris(4-carboxyphenyl)benzene (1,3,5-Tris(4- It may be one or more selected from carboxyphenyl)benzene; H 3 BTB).
본 발명에서, 상기 부직포 섬유는 녹는점이 115℃ 이상인 것일 수 있다. 상기 부직포 섬유의 녹는점이 115℃ 미만일 경우, 상기 구리 기반 배위 고분자 입자가 상기 부직포 표면에 코팅되는 과정에서 변성이 일어날 수 있다.In the present invention, the nonwoven fabric may have a melting point of 115° C. or higher. When the melting point of the nonwoven fiber is less than 115° C., denaturation may occur while the copper-based coordination polymer particles are coated on the surface of the nonwoven fabric.
본 발명에서, 상기 부직포 섬유는 축합폴리머 소재일 수 있고, 바람직하게는 폴리에스테르 및 폴리아미드에서 선택된 어느 하나 이상일 수 있다. 모노머의 축합중합에 의해 제조된 상기 축합폴리머는 모노머의 첨가중합에 의해 제조된 폴리머에 비해 내열성이 높은 효과를 가져 안정적으로 흡착제의 표면 구조를 제공할 수 있다.In the present invention, the nonwoven fabric fiber may be a condensed polymer material, preferably at least one selected from polyester and polyamide. The condensation polymer prepared by condensation polymerization of monomers has a higher heat resistance effect than the polymer prepared by addition polymerization of monomers, and can stably provide a surface structure of the adsorbent.
본 발명에서, 상기 기체는 휘발성 유기 화합물 및 이산화탄소에서 선택된 어느 하나 이상을 포함하는 것일 수 있고, 바람직하게는 상기 휘발성 유기 화합물은 방향족 화합물(aromatic compounds)일 수 있다.In the present invention, the gas may include at least one selected from volatile organic compounds and carbon dioxide, and preferably, the volatile organic compounds may be aromatic compounds.
본 발명에서, 휘발성 유기 화합물은 벤젠, 에틸렌글리콜, 포름알데히드, 메틸렌클로라이드, 테트라클로로에틸렌, 톨루엔, 자일렌 및 1,3-부타디엔에서 선택된 어느 하나 이상인 것일 수 있고, 더욱 바람직하게는 p-자일렌(p-Xylene)일 수 있다. 상기 휘발성 유기 화합물 및 이산화탄소는 본 발명의 구리 기반 배위 고분자 입자 표면에 포획 또는 흡수되어 공기의 질을 향상시킬 수 있다.In the present invention, the volatile organic compound may be any one or more selected from benzene, ethylene glycol, formaldehyde, methylene chloride, tetrachloroethylene, toluene, xylene and 1,3-butadiene, more preferably p-xylene (p-Xylene). The volatile organic compound and carbon dioxide can be captured or absorbed on the surface of the copper-based coordination polymer particle of the present invention to improve air quality.
본 발명의 다른 일 실시예에 따라, 구리 기반 배위 고분자 입자를 포함하는 용액에 부직포 섬유를 담그는 단계; 115℃ 내지 140℃에서 4시간 내지 12시간 동안 처리하는 단계; 및 세척 및 건조하는 단계;를 포함하는, 흡착제 제조방법이 제공될 수 있다. 상기 처리하는 단계에서, 처리 온도가 115℃ 미만일 경우 반응이 충분히 일어나지 않을 수 있고, 140℃ 이상일 경우 상기 구리 기반 배위 고분자 입자가 고르게 분포되지 않아 표면적이 극대화되지 않을 수 있다. 또한, 상기 처리하는 단계에서, 처리 시간이 4시간 미만일 경우 반응이 충분히 일어나지 않을 수 있고, 12시간 이상일 경우 상기 구리 기반 배위 고분자 입자의 표면적이 극대화되지 않을 수 있다.According to another embodiment of the present invention, immersing the non-woven fabric fibers in a solution containing copper-based coordination polymer particles; processing at 115° C. to 140° C. for 4 to 12 hours; And washing and drying; containing, an adsorbent manufacturing method may be provided. In the treatment step, when the treatment temperature is less than 115 ° C., the reaction may not sufficiently occur, and when the treatment temperature is higher than 140 ° C., the surface area may not be maximized because the copper-based coordination polymer particles are not evenly distributed. Further, in the treatment step, if the treatment time is less than 4 hours, the reaction may not sufficiently occur, and if the treatment time is more than 12 hours, the surface area of the copper-based coordination polymer particles may not be maximized.
본 발명에서, 상기 구리 기반 배위 고분자 입자는 1 또는 4개의 방향족 고리를 갖는 리간드를 포함하는 것일 수 있다.In the present invention, the copper-based coordination polymer particle may include a ligand having 1 or 4 aromatic rings.
본 발명에서 상기 구리 기반 배위 고분자 입자는 앞서 기술한 화학식 1 내지 2에서 선택된 어느 하나인 것일 수 있고, 바람직하게는 앞서 기술한 화학식 3 내지 5에서 선택된 어느 하나인 것일 수 있다.In the present invention, the copper-based coordination polymer particle may be any one selected from Chemical Formulas 1 to 2 described above, preferably any one selected from Chemical Formulas 3 to 5 described above.
본 발명에서, 상기 부직포 섬유는 녹는점이 115℃ 이상인 것일 수 있다. 상기 부직포 섬유의 녹는점이 115℃ 미만일 경우, 구리 기반 배위 고분자 입자가 상기 부직포 표면에 코팅되기 위하여 상기 처리되는 과정에서 변성이 일어날 수 있다.In the present invention, the nonwoven fabric may have a melting point of 115° C. or higher. When the melting point of the nonwoven fabric is less than 115° C., modification may occur during the treatment so that the copper-based coordination polymer particles are coated on the surface of the nonwoven fabric.
본 발명에서, 상기 기체는 휘발성 유기 화합물 및 이산화탄소에서 선택된 어느 하나 이상을 포함하는 것일 수 있다.In the present invention, the gas may include at least one selected from volatile organic compounds and carbon dioxide.
본 발명에서, 생략된 나머지 기재들은 앞서 기재된 구리 기반 배위 고분자 입자가 표면에 코팅된 부직포 섬유를 포함하는 흡착제와 마찬가지로 해석될 수 있다.In the present invention, the remaining descriptions omitted can be interpreted in the same way as the adsorbent including nonwoven fibers coated on the surface of the copper-based coordination polymer particles described above.
본 발명의 또 다른 일 실시예에 따라, 본 발명의 방법에 의해 제조된 흡착제가 제공될 수 있다.According to another embodiment of the present invention, an adsorbent prepared by the method of the present invention may be provided.
본 발명의 또 다른 일 실시예에 따라, 본 발명의 흡착제를 포함하는 여과막, 여과기, 공기청정기, 에어컨, 공기조화기 등이 제공될 수 있다.According to another embodiment of the present invention, a filtration membrane, a filter, an air purifier, an air conditioner, an air conditioner, and the like including the adsorbent of the present invention may be provided.
이하, 실시예를 통해 본 발명을 더욱 상술하나 하기 실시예에 의해 본 발명이 제한되지 아니함은 자명하다. Hereinafter, the present invention is further detailed through examples, but it is obvious that the present invention is not limited by the following examples.
제조예 1Preparation Example 1
도 1을 참조하여, 구리 기반 배위 고분자 입자(Cu-CPP)로 데코레이트된 부직포 섬유(NWF) 표면을 정상 소재 성장 방법(in situ growth method)에 의해 합성되었다. 구체적으로는 2.18g의 Cu(NO3)2.3H2O를 60mL의 수용액에 용해시킨 다음 유기 리간드로 트라이메스산(Trimesic acid) 1.05g을 포함하는 60mL의 에탄올 용액을 부었다. 혼합 용액을 4분 동안 볼텍싱하고, 흔들고, 초음파 처리하였다. 다음으로 길이 16cm, 너비 12cm의 깨끗한 부직포 섬유(NWF)를 용액에 완전히 담그어 구리 기반 배위 고분자 입자(Cu-CPP)가 로드되어 담금 피막법(dip-coating method)을 준비하였다. 상기 부직포 섬유에서 Cu-CPP의 성장은 열수 합성 오토클레이브 반응기를 사용하여 120℃, 6시간 동안 수행되었다. 완료 후 최종 생성물인 Cu-CPP/NWF를 에탄올로 여러 번 세척하여 잔류 반응물을 제거하고 실온에서 진공 건조하였다.Referring to FIG. 1 , the surface of nonwoven fibers (NWF) decorated with copper-based coordinating polymer particles (Cu-CPP) was synthesized by an in situ growth method. Specifically, 2.18 g of Cu(NO 3 ) 2 .3H 2 O was dissolved in 60 mL of an aqueous solution, and then 60 mL of an ethanol solution containing 1.05 g of trimesic acid as an organic ligand was poured. The mixed solution was vortexed, shaken, and sonicated for 4 minutes. Next, a clean nonwoven fabric (NWF) with a length of 16 cm and a width of 12 cm was completely immersed in the solution, and copper-based coordination polymer particles (Cu-CPP) were loaded to prepare a dip-coating method. The growth of Cu-CPP on the nonwoven fabric was performed at 120° C. for 6 hours using a hydrothermal synthesis autoclave reactor. After completion, the final product, Cu-CPP/NWF, was washed several times with ethanol to remove residual reactants, and dried under vacuum at room temperature.
도 1에서 나타난 바와 같이, 흰색의 부직포 섬유(NWF) 표면에 구리 기반 배위 고분자 입자(Cu-CPP)가 형성되어 밝은 파란색으로 변화된 것(Cu-CPP/NWF)을 확인하였다.As shown in FIG. 1, it was confirmed that copper-based coordination polymer particles (Cu-CPP) were formed on the surface of the white nonwoven fabric fiber (NWF) and changed to bright blue (Cu-CPP/NWF).
제조예 2Preparation Example 2
제조예 2의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 부직포 섬유 소재로 폴리아미드를 사용하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Preparation Example 2, the normal material growth method of Preparation Example 1 was used, but polyamide was used as a nonwoven fiber material.
제조예 3Preparation Example 3
제조예 3의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 부직포 섬유 소재로 폴리카보네이트를 사용하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Preparation Example 3, the normal material growth method of Preparation Example 1 was used, but polycarbonate was used as a nonwoven fiber material.
제조예 4Production Example 4
제조예 4의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 1,3,5-트리스(브로모메틸)-2,4,6-트리메틸벤젠(1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene; C12H15Br3)을 사용하여 Cu-CPP를 제조하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Preparation Example 4, the normal material growth method of Preparation Example 1 was used, but 1,3,5-tris (bromomethyl) -2,4, Cu-CPP was prepared using 6-trimethylbenzene (1,3,5-Tris(bromomethyl)-2,4,6-trimethylbenzene; C 12 H 15 Br 3 ).
제조예 5Preparation Example 5
제조예 5의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 1,3,5-트리스(4-카르복시페닐)벤젠(1,3,5-Tris(4-carboxyphenyl)benzene; H3BTB)을 사용하여 Cu-CPP를 제조하였다.In order to prepare the copper-based coordination polymer particle (Cu-CPP) surface of Preparation Example 5, the normal material growth method of Preparation Example 1 was used, but 1,3,5-tris (4-carboxyphenyl) benzene (1, Cu-CPP was prepared using 3,5-Tris(4-carboxyphenyl)benzene; H 3 BTB).
비교예 1Comparative Example 1
비교예 1의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 부직포 섬유 소재로 폴리에틸렌을 사용하였고, 오토클레이브 반응기에서 105℃, 6시간 동안 Cu-CPP를 성장시켰다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 1, the normal material growth method of Preparation Example 1 was used, but polyethylene was used as a nonwoven fiber material, and 105 ° C., 6 Cu-CPP was grown over time.
비교예 2Comparative Example 2
비교예 2의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 부직포 섬유 소재로 폴리프로필렌을 사용하였고, 오토클레이브 반응기에서 105℃, 6시간 동안 Cu-CPP를 성장시켰다.In order to prepare the copper-based coordination polymer particle (Cu-CPP) surface of Comparative Example 2, the normal material growth method of Preparation Example 1 was used, but polypropylene was used as a nonwoven fiber material, and 105 ° C. in an autoclave reactor, Cu-CPP was grown for 6 hours.
비교예 3Comparative Example 3
비교예 3의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 오토클레이브 반응기에서 120℃, 3시간 동안 Cu-CPP를 성장시켰다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 3, the normal material growth method of Preparation Example 1 was used, but Cu-CPP was grown in an autoclave reactor at 120 ° C. for 3 hours.
비교예 4Comparative Example 4
비교예 4의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 오토클레이브 반응기에서 120℃, 20시간 동안 Cu-CPP를 성장시켰다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 4, the normal material growth method of Preparation Example 1 was used, but Cu-CPP was grown in an autoclave reactor at 120 ° C. for 20 hours.
비교예 5Comparative Example 5
비교예 5의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 오토클레이브 반응기에서 160℃에서 6시간동안 Cu-CPP를 성장시켰다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 5, the normal material growth method of Preparation Example 1 was used, but Cu-CPP was grown at 160 ° C. for 6 hours in an autoclave reactor.
비교예 6Comparative Example 6
비교예 6의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 유기 리간드로 4,4′-옥시비스벤조산(oxybis benzoic acid; H2Oba)을 사용하여 Cu-CPP를 제조하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 6, the normal material growth method of Preparation Example 1 was used, but 4,4′-oxybis benzoic acid (H 2 Oba) was used to prepare Cu-CPP.
비교예 7Comparative Example 7
비교예 7의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 유기 리간드로 2,5-디히드록시테레프탈산(2,5-dihydroxyterephthalic acid; dhtp)을 사용하여 Cu-CPP를 제조하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 7, the normal material growth method of Preparation Example 1 was used, but 2,5-dihydroxyterephthalic acid (2,5-dihydroxyterephthalic acid) was used as an organic ligand. acid; dhtp) was used to prepare Cu-CPP.
비교예 8Comparative Example 8
비교예 8의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 유기 리간드로 푸마릭산을 사용하여 Cu-CPP를 제조하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 8, the normal material growth method of Preparation Example 1 was used, but Cu-CPP was prepared using fumaric acid as an organic ligand.
비교예 9Comparative Example 9
비교예 9의 구리 기반 배위 고분자 입자(Cu-CPP) 표면을 제조하기 위하여, 상기 제조예 1의 정상 소재 성장 방법을 사용하되, 유기 리간드로 프로페인다이온산을 사용하여 Cu-CPP를 제조하였다.In order to prepare the surface of the copper-based coordination polymer particles (Cu-CPP) of Comparative Example 9, the normal material growth method of Preparation Example 1 was used, but Cu-CPP was prepared using propanedioic acid as an organic ligand.
실험예 1Experimental Example 1
상기 제조예 1 내지 5, 비교예 1 내지 9 및 활성탄의 흡착 능력을 비교하기 위하여, 브루나우어-에멋-텔러 표면적(Brunauer-Emmett-Teller Surface Area; BET 표면적; SBET), 공극 부피(VBJH) 및 평균 공극 지름을 측정하여 하기 표 1 내지 3에 나타내었다.In order to compare the adsorption capacities of Preparation Examples 1 to 5, Comparative Examples 1 to 9 and activated carbon, Brunauer-Emmett-Teller Surface Area (BET surface area; SBET), void volume (VBJH) And the average pore diameter was measured and shown in Tables 1 to 3 below.
항목Item 제조예 1Preparation Example 1 제조예 2Preparation Example 2 제조예 3Preparation Example 3 제조예 4Production Example 4 제조예 5Preparation Example 5
유기 리간드organic ligands 트라이메스산trimesic acid 트라이메스산trimesic acid 트라이메스산trimesic acid C12H15Br3 C 12 H 15 Br 3 H3BTBH 3 BTB
부직포 섬유 소재non-woven textile material 폴리에스테르Polyester 폴리아미드polyamide 폴리카보네이트polycarbonate 폴리에스테르Polyester 폴리에스테르Polyester
성장 조건growing conditions 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours
SBET(m2)SBET(m 2 ) 1318.11318.1 1316.11316.1 1185.01185.0 1063.41063.4 912.3912.3
VBJH (cm3/g)VBJH (cm 3 /g) 0.530.53 0.400.40 0.430.43 0.480.48 0.460.46
평균 공극 지름(Å)Average pore diameter (Å) 16.1416.14 17.2217.22 14.6714.67 12.4412.44 13.4213.42
항목Item 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5
유기 리간드organic ligands 트라이메스산trimesic acid 트라이메스산trimesic acid 트라이메스산trimesic acid 트라이메스산trimesic acid 트라이메스산trimesic acid
부직포 섬유 소재non-woven textile material 폴리에틸렌polyethylene 폴리프로필렌polypropylene 폴리에스테르Polyester 폴리에스테르Polyester 폴리에스테르Polyester
성장 조건growing conditions 105℃, 6시간105℃, 6 hours 105℃, 6시간105℃, 6 hours 120℃, 3시간120℃, 3 hours 120℃, 20시간120℃, 20 hours 160℃, 6시간160℃, 6 hours
SBET(m2)SBET(m 2 ) 631.50631.50 764.1764.1 445.0445.0 715.9715.9 1042.81042.8
VBJH (cm3/g)VBJH (cm 3 /g) 0.310.31 0.350.35 0.210.21 0.300.30 0.390.39
평균 공극 지름(Å)Average pore diameter (Å) 11.2111.21 10.6110.61 11.2511.25 11.5611.56 11.4111.41
항목Item 비교예 6Comparative Example 6 비교예 7Comparative Example 7 비교예 8Comparative Example 8 비교예 9Comparative Example 9 활성탄activated carbon
유기 리간드organic ligands H2OBaH 2 OBa dhtpdhtp 푸마릭산fumaric acid 프로페인다이온산propanedioic acid --
부직포 섬유 소재non-woven textile material 폴리에스테르Polyester 폴리에스테르Polyester 폴리에스테르Polyester 폴리에스테르Polyester --
성장 조건growing conditions 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours 120℃, 6시간120℃, 6 hours --
SBET(m2)SBET(m 2 ) 448.8448.8 408.5408.5 306.8306.8 416.2416.2 526.80526.80
VBJH (cm3/g)VBJH (cm 3 /g) 0.410.41 0.490.49 0.370.37 0.430.43 0.290.29
평균 공극 지름(Å)Average pore diameter (Å) 6.746.74 8.508.50 4.574.57 5.655.65 22.2522.25
상기 표 1 내지 3에서 나타난 바와 같이, 제조예 1 내지 5의 BET 표면적(SBET)은 1,200m2/g 이상, 기공 부피(VBJH)는 0.4cm2/g 이상으로, 이는 비교예 1 내지 9 및 활성탄의 BET 표면적 및 기공 부피에 비해 현저히 높은 수치이며, 제조예 1 내지 5의 평균 공극 지름 역시 12Å 이상으로, 비교예 1 내지 9에 비하여 현저히 높은 수치인 바, 트라이메스산 또는 dhtp 유기 리간드를 사용하여 Cu-CPP를 제조한 후 폴리에스테르, 폴리아미드, 폴리카보네이트 또는 폴리페닐렌옥사이드 소재의 부직포 섬유 소재에 120℃, 6시간 성장시킨 구리 표면의 경우, 표면 특성이 뛰어난 효과를 확인할 수 있었다.As shown in Tables 1 to 3, the BET surface area (SBET) of Preparation Examples 1 to 5 is 1,200 m 2 /g or more and the pore volume (VBJH) is 0.4 cm 2 /g or more, which is comparable to Comparative Examples 1 to 9 and This is a significantly higher value than the BET surface area and pore volume of activated carbon, and the average pore diameter of Preparation Examples 1 to 5 is also 12 Å or more, which is significantly higher than that of Comparative Examples 1 to 9. Use of trimesic acid or dhtp organic ligand After manufacturing Cu-CPP, the effect of excellent surface properties was confirmed in the case of the copper surface grown on polyester, polyamide, polycarbonate or polyphenylene oxide nonwoven fiber material at 120 ° C. for 6 hours.
실험예 2Experimental Example 2
실시예 1에 따라 Cu-CPP 코팅을 하기 전 부직포 섬유(NWF)의 표면 형태를 주사 전자 현미경(SEM)으로 확인하여 도 2와 같이 나타내었고, Cu-CPP 코팅을 한 후 부직포 섬유(NWF)의 표면 형태를 주사 전자 현미경(SEM)으로 확인하여 도 3과 같이 나타내었다.According to Example 1, the surface morphology of the nonwoven fabric (NWF) before the Cu-CPP coating was confirmed with a scanning electron microscope (SEM) and shown in FIG. 2, and the surface morphology of the nonwoven fabric (NWF) after the Cu-CPP coating The surface morphology was confirmed with a scanning electron microscope (SEM) and shown in FIG. 3 .
도 2에 나타난 것처럼, Cu-CPP 코팅 전 부직포 섬유의 경우 깨끗하고 매끄러운 표면과 물결 모양의 채널을 나타내었고, 도 3에 나타난 것처럼, 실시예 1에 따라 Cu-CPP 코팅을 한 후 결과물에서는 Cu-CPP 마이크로 결정의 외관이 명확하게 감지되었다. 상기 Cu-CPP 결정은 부직포 섬유(NWF)를 조밀하게 덮고 있으며 개별적으로 8면체 토폴로지를 사용하여 직경이 약 12μm 정도로 나타났다.As shown in FIG. 2, the nonwoven fabric before Cu-CPP coating showed a clean and smooth surface and a wavy channel, and as shown in FIG. 3, after Cu-CPP coating according to Example 1, the result showed Cu- The appearance of CPP microcrystals was clearly detected. The Cu-CPP crystals densely covered the non-woven fabric (NWF) and each had a diameter of about 12 μm using an octahedral topology.
실험예 3Experimental Example 3
실시예 1에 따라 Cu-CPP 코팅을 한 후 Cu-CPP/NWF의 에너지 분산 스펙트럼 (energy-dispersive spectrum; EDS) 매핑을 실시하여 도 4와 같이 나타내었다.After Cu-CPP coating according to Example 1, energy-dispersive spectrum (EDS) mapping of Cu-CPP/NWF was performed and shown in FIG. 4 .
도 4에 나타난 것처럼, 부직포 섬유를 형성하는 주요 원소인 탄소와 산소 피크가 표시되었고 구리 피크 역시 표시되어, 상기 Cu-CPP/NWF를 구성하는 모든 원소가 필터의 전체 표면에 균일하게 분포된 것으로 나타난 바, Cu-CPP가 부직포 섬유에서 성공적으로 성장한 것을 확인할 수 있었다.As shown in FIG. 4, the peaks of carbon and oxygen, which are the main elements forming nonwoven fabric fibers, are displayed, and the peak of copper is also displayed, indicating that all elements constituting the Cu-CPP/NWF are uniformly distributed over the entire surface of the filter. Bar, it was confirmed that Cu-CPP was successfully grown on nonwoven fabric fibers.
실험예 4Experimental Example 4
실시예 1에 따라 Cu-CPP 코팅을 한 후 Cu-CPP/NWF 구조의 결정도를 추가로 평가하고 부직포 섬유에서 Cu-CPP의 존재를 확인하기 위하여, X-선 회절(XRD) 분석을 실시한 결과를 도 5에 나타내었다.In order to further evaluate the crystallinity of the Cu-CPP/NWF structure after Cu-CPP coating according to Example 1 and to confirm the presence of Cu-CPP in nonwoven fibers, the results of X-ray diffraction (XRD) analysis were performed. shown in Figure 5.
도 5에서 나타난 바와 같이. Cu-CPP에 의한 2θ = 6.7°, 9.5°, 11.6°, 13.4°, 14.6°, 17.3°, 18.9°, 25.8° 및 29.2°에서 회절 피크가 나타난 바, 부직포 섬유 필터에서 결정질 Cu-CPP가 성공적으로 성장한 것을 확인하였다.As shown in Figure 5. As the diffraction peaks at 2θ = 6.7°, 9.5°, 11.6°, 13.4°, 14.6°, 17.3°, 18.9°, 25.8° and 29.2° by Cu-CPP were observed, crystalline Cu-CPP was successfully growth was confirmed.
실험예 5Experimental Example 5
BET 표면적의 변화에 따른 질소 기체 흡수 능력을 평가하였다. 구체적으로는 제조예 1에 따른 Cu-CPP/NWF(또는 Cu-CPP 마이크로 결정) 및 비교예 3에 따른 Cu-CPP/NWF 및 구리 코팅되지 않은 부직포 섬유 각각의 질소 기체 흡수 등온선을 측정하여 도 6에 나타내었다.The nitrogen gas absorption ability according to the change of the BET surface area was evaluated. Specifically, nitrogen gas absorption isotherms of Cu-CPP/NWF (or Cu-CPP microcrystals) according to Preparation Example 1 and Cu-CPP/NWF according to Comparative Example 3 and non-woven fabric fibers without copper coating were measured, and FIG. 6 shown in
도 6에 나타난 바와 같이, 제조예 1과 같이 BET 표면적이 약 1,318m2/g인 경우, 비교예 1과 같이 BET 표면적이 약 445m2/g인 경우에 비하여 3배 정도의 질소 기체 흡수 능력을 가지는 바, BET 표면적이 큰 경우 Cu-CPP/NWF의 필터 기능이 큰 것을 확인할 수 있었다.As shown in FIG. 6, when the BET surface area is about 1,318 m 2 /g as in Preparation Example 1, the nitrogen gas absorption capacity is three times greater than when the BET surface area is about 445 m 2 /g like in Comparative Example 1. As a result, it was confirmed that the filter function of Cu-CPP/NWF was large when the BET surface area was large.
실험예 6Experimental Example 6
Cu-CPP/NWF의 p-자일렌 흡착 효율을 확인하기 위하여 도 7과 같이 유동 흡착 장비를 사용하여 검사하였다. 구체적으로는, 유량조절기를 사용하여 p-자일렌 오염물질(서울 특수 가스 Co., Ltd.)의 농도를 4ppm/분으로 조정하였다. 공기와 상기 p-자일렌과 같은 휘발성 유기 화합물(VOCs)의 혼합물은 총 유속이 50mL/분으로 인라인 스테틱 믹서(inline static mixer)로 운반되었다. 관형 흐름조(Plug Flow Reactor; PFR) (390x90x40mm3, 대한민국 Chemre)는 흡수제로 사용된 Cu-CPP/NWF 필터를 포장하는 데 사용되었다. 상기 Cu-CPP/NWF 필터는 제조예 1에 의해 제조된 것을 사용하였고, 실험 조건은 25℃(298K), RH = 0%에서 수행되었다. 대조구로는 부직포 섬유(NWF)를 사용하여 흡수된 p-자일렌의 양을 GC/MS로 측정하여 도 8 및 도 9에 나타내었다.In order to confirm the p-xylene adsorption efficiency of Cu-CPP/NWF, it was examined using a flow adsorption equipment as shown in FIG. 7 . Specifically, the concentration of p-xylene contaminants (Seoul Special Gas Co., Ltd.) was adjusted to 4 ppm/min using a flow controller. A mixture of air and volatile organic compounds (VOCs) such as p-xylene was delivered to an inline static mixer at a total flow rate of 50 mL/min. A Plug Flow Reactor (PFR) (390x90x40 mm 3 , Chemre, Korea) was used to pack the Cu-CPP/NWF filter used as the absorbent. The Cu-CPP/NWF filter was used as prepared in Preparation Example 1, and the experimental conditions were performed at 25° C. (298K) and RH = 0%. As a control, the amount of p-xylene absorbed by using nonwoven fabric (NWF) was measured by GC/MS and shown in FIGS. 8 and 9 .
도 8 및 도 9에 나타난 바와 같이, 대조구로 사용된 부직포 섬유(NWF)는 흡수 능력이 없는데 비하여, Cu-CPP/NWF 필터는 350분 동안 최대 100% p-자일렌을 흡수하여, 발암성 휘발성 유기 화합물을 오염 제거를 위한 고효율 및 친환경 공정에 활용할 수 있음을 확인하였다.As shown in FIGS. 8 and 9, the nonwoven fabric (NWF) used as a control has no absorption capacity, whereas the Cu-CPP/NWF filter absorbs up to 100% p-xylene for 350 minutes, reducing carcinogenic volatility. It was confirmed that organic compounds can be utilized in high-efficiency and eco-friendly processes for decontamination.
실험예 7Experimental Example 7
도 10은 Cu-CPP가 p-자일렌을 흡착하는 메커니즘을 나타낸 것이다. 구리 양이온으로 구성된 Cu-CPP는 노드의 연결 중심으로서 p-자일렌의 방향족과 금속 사이의 양이온-π 상호 작용을 통해 흡착할 수 있으므로, 본 발명의 Cu-CPP는 휘발성 유기 화합물 오염 물질 흡착 효과가 있음을 확인할 수 있었다. 이온 또한 Cu-CPP는 유기 링커로 1,3,5-벤젠트리카복실산을 가지고 있는데, 이는 p-자일렌의 페닐 고리와 Cu-CPP 구조 사이의 π-π 상호 작용으로 인해 흡착에 효과적으로 작용하였다. 더욱이, Cu-CPP의 큰 공동과 풍부한 가스 흡수 위치는 매우 높은 표면적과 함께 오염 물질의 흡착에 긍정적인 기여를 제공하였다.10 shows the mechanism by which Cu-CPP adsorbs p-xylene. Since Cu-CPP composed of copper cations can be adsorbed through the cation-π interaction between the aromatics of p-xylene and the metal as the connecting center of the node, the Cu-CPP of the present invention has an adsorption effect of volatile organic compound contaminants. it was possible to confirm that In addition, Cu-CPP has 1,3,5-benzene tricarboxylic acid as an organic linker, which was effective for adsorption due to the π-π interaction between the phenyl ring of p-xylene and the Cu-CPP structure. Moreover, the large cavities and rich gas adsorption sites of Cu-CPP together with the very high surface area provided a positive contribution to the adsorption of contaminants.
실험예 8Experimental Example 8
BET 표면적의 변화에 따른 이산화탄소 기체 흡수 능력을 평가하였다. 구체적으로는 구체적으로는 제조예 1에 따른 Cu-CPP/NWF(또는 Cu-CPP 마이크로 결정) 및 비교예 3에 따른 Cu-CPP/NWF 및 구리 코팅되지 않은 NWF 각각이 0bar 내지 1bar에서 이산화탄소를 흡수하는 능력을 확인하여 도 11에 나타내었다.The carbon dioxide gas absorbing ability according to the change of the BET surface area was evaluated. Specifically, Cu-CPP/NWF (or Cu-CPP microcrystals) according to Preparation Example 1 and Cu-CPP/NWF and non-copper coated NWF according to Comparative Example 3 respectively absorb carbon dioxide at 0 bar to 1 bar. The ability to do was confirmed and shown in Figure 11.
도 11에 나타난 바와 같이, 순수한 부직포 섬유는 이산화탄소 흡착 활성이 없는 반면, Cu-CPP 마이크로 결정은 상대적으로 34.47cm3/g의 높은 흡착 용량으로 우수한 흡착 성능을 나타내었다. 그러나, Cu-CPP 마이크로 결정은 분말 형태이므로 파이프를 막고 실제 적용에서 큰 가스 저항을 일으킬 수 있으므로 동적 프로세스 및 실제 적용에서 Cu-CPP/NWF를 사용하는 것이 바람직하다. 비교예 3의 경우, 19.81cm3/g의 흡착 용량을 가져, 순수한 부직포 섬유에 비해 높은 이산화탄소 흡착 용량을 가지는 것을 확인하였다.As shown in FIG. 11 , the pure nonwoven fabric had no carbon dioxide adsorption activity, whereas the Cu-CPP microcrystals showed excellent adsorption performance with a relatively high adsorption capacity of 34.47 cm 3 /g. However, since Cu-CPP microcrystals are in powder form, they can clog pipes and cause large gas resistance in practical applications, so it is preferable to use Cu-CPP/NWF in dynamic processes and practical applications. In the case of Comparative Example 3, it had an adsorption capacity of 19.81 cm 3 /g, and it was confirmed that it had a higher carbon dioxide adsorption capacity than pure nonwoven fabric fibers.
실험예 9Experimental Example 9
도 12는 Cu-CPP의 이산화탄소 흡착 메커니즘을 모식도로 나타낸 것이다. 상기 이산화탄소 흡착 메커니즘은 섬유에 증착된 Cu-CPP의 높은 다공성, 큰 비표면적 및 풍부한 개방 금속 사이트로 확인되었다. 그 중 Cu-CPP의 이산화탄소 흡착 메커니즘에 기여한 두 개의 주요 흡착 사이트는 열린 금속 사이트와 작은 케이지 창 사이트이다. 상기 사이트는 첫째, 열린 금속 이온은 패들휠 구조(paddlewheel structure)를 통하여 동등하게 불포화된 구리 이온 중심을 노출시킬 수 있었고, 이는 정전기 상호 작용을 통한 이산화탄소의 분극화 및 이산화탄소가 사중극성 모멘트를 크게 가지도록 유도하여, 가장 강한 결합 부위를 가지는 것에 기여하였다. 둘째, 적절한 창 크기를 가진 고유 공동을 통해 우선적으로 이산화탄소 분자를 포획할 수 있었다.12 is a schematic diagram showing the carbon dioxide adsorption mechanism of Cu-CPP. The carbon dioxide adsorption mechanism was confirmed by the high porosity, large specific surface area and abundant open metal sites of the Cu-CPP deposited on the fibers. Among them, the two major adsorption sites contributing to the carbon dioxide adsorption mechanism of Cu-CPP are open metal sites and small cage window sites. The site was, firstly, that open metal ions could expose equally unsaturated copper ion centers through a paddlewheel structure, which led to the polarization of carbon dioxide through electrostatic interactions and to make carbon dioxide have a large quadrupole moment. induced, contributing to having the strongest binding site. Second, it was possible to preferentially trap carbon dioxide molecules through a unique cavity with an appropriate window size.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시예일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. Having described specific parts of the present invention in detail above, it will be clear to those skilled in the art that these specific descriptions are merely preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
본 발명은 안정적으로 이산화탄소를 포집하고 및 휘발성 유기 화합물을 흡수하기 위한 구리 기반 배위 고분자 입자 표면 및 이의 제조방법을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a copper-based coordinated polymer particle surface for stably capturing carbon dioxide and absorbing volatile organic compounds and a method for preparing the same.

Claims (12)

  1. 구리 기반 배위 고분자 입자가 표면에 코팅된 부직포 섬유를 포함하는 기체 흡착제.A gas adsorbent comprising nonwoven fibers coated on the surface of copper-based coordinating polymer particles.
  2. 제1항에 있어서, According to claim 1,
    상기 구리 기반 배위 고분자 입자는 1 또는 4개의 방향족 고리를 갖는 리간드를 포함하는 것인, 흡착제.The copper-based coordination polymer particles include a ligand having 1 or 4 aromatic rings, the adsorbent.
  3. 제2항에 있어서, According to claim 2,
    상기 리간드는 하기 화학식 1 내지 2로 표시되는 것에서 선택된 어느 하나 이상인, 흡착제:The ligand is any one or more selected from those represented by the following formulas 1 to 2, the adsorbent:
    [화학식 1][Formula 1]
    Figure PCTKR2022002753-appb-img-000008
    Figure PCTKR2022002753-appb-img-000008
    [화학식 2][Formula 2]
    Figure PCTKR2022002753-appb-img-000009
    Figure PCTKR2022002753-appb-img-000009
    상기 화학식 1 내지 2에서,In Formulas 1 and 2,
    R1은 -F, -Cl, -Br, -I, -S-, -O-, -NO2, -CN, -SO3 -, -COO- 또는 -COCl-이고;R 1 is -F, -Cl, -Br, -I, -S - , -O - , -NO 2 , -CN, -SO 3 - , -COO - or -COCl - ;
    R2 내지 R4는 서로 독립적으로 -H, -CH3 또는 -C2H5이고;R 2 to R 4 are each independently -H, -CH 3 or -C 2 H 5 ;
    p는 0 내지 3이다. p is 0 to 3;
  4. 제1항에 있어서, According to claim 1,
    상기 부직포 섬유는 녹는점이 115℃ 이상인 것인, 흡착제.The non-woven fabric is an adsorbent having a melting point of 115 ° C or higher.
  5. 제1항에 있어서, According to claim 1,
    상기 부직포 섬유는 축합폴리머 소재인, 흡착제.The non-woven fiber is a condensation polymer material, an adsorbent.
  6. 제1항에 있어서, According to claim 1,
    상기 기체는 휘발성 유기 화합물 및 이산화탄소에서 선택된 어느 하나 이상을 포함하는 것인, 흡착제.The adsorbent, wherein the gas contains at least one selected from volatile organic compounds and carbon dioxide.
  7. 구리 기반 배위 고분자 입자를 포함하는 용액에 부직포 섬유를 담그는 단계; immersing the non-woven fibers in a solution containing copper-based coordinating polymer particles;
    115℃ 내지 140℃에서 4시간 내지 12시간동안 처리하는 단계; 및 processing at 115° C. to 140° C. for 4 to 12 hours; and
    세척 및 건조하는 단계;를 포함하는, 기체 흡착제 제조방법.A method for preparing a gas adsorbent comprising the steps of washing and drying.
  8. 제7항에 있어서, According to claim 7,
    상기 구리 기반 배위 고분자 입자는 1 또는 4개의 방향족 고리를 갖는 리간드를 포함하는 것인, 흡착제 제조방법.Wherein the copper-based coordination polymer particles include a ligand having 1 or 4 aromatic rings.
  9. 제7항에 있어서, According to claim 7,
    상기 기체는 휘발성 유기 화합물 및 이산화탄소에서 선택된 어느 하나 이상을 포함하는 것인, 흡착제 제조방법.Wherein the gas contains at least one selected from volatile organic compounds and carbon dioxide.
  10. 제7항 내지 제9항 중 어느 한 항의 방법에 의해 제조된, 흡착제.An adsorbent prepared by the method of any one of claims 7 to 9.
  11. 제1항 내지 제6항 및 제10항 중 어느 한 항의 흡착제를 포함하는 공기청정기.An air purifier comprising the adsorbent of any one of claims 1 to 6 and 10.
  12. 제1항 내지 제6항 및 제10항 중 어느 한 항의 흡착제를 포함하는 공기조화기.An air conditioner comprising the adsorbent of any one of claims 1 to 6 and 10.
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