KR20190009541A - Novel nanocomposite and preparation method thereof - Google Patents
Novel nanocomposite and preparation method thereof Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002086 nanomaterial Substances 0.000 claims abstract description 41
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910021389 graphene Inorganic materials 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- -1 fluorographene Chemical compound 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- GMMSTIGHDDLCMI-UHFFFAOYSA-N zinc;imidazol-3-ide Chemical group [Zn+2].C1=C[N-]C=N1.C1=C[N-]C=N1 GMMSTIGHDDLCMI-UHFFFAOYSA-N 0.000 description 26
- 239000012621 metal-organic framework Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 4
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910016001 MoSe Inorganic materials 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001786 chalcogen compounds Chemical class 0.000 description 1
- 150000001787 chalcogens Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960002017 echothiophate Drugs 0.000 description 1
- BJOLKYGKSZKIGU-UHFFFAOYSA-N ecothiopate Chemical compound CCOP(=O)(OCC)SCC[N+](C)(C)C BJOLKYGKSZKIGU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 210000004894 snout Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
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Abstract
Description
본 발명은 신규한 나노복합체 및 그 제조방법에 관한 것으로, 보다 상세하게는 수십 나노미터 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재 상에 금속-유기 구조체를 성장시킴으로써 표면적이 현저하게 향상된 나노복합체를 제조하고, 이를 센서, 촉매 및 분리막 등에 응용하는 기술에 관한 것이다.
The present invention relates to a novel nanocomposite and a method for producing the nanocomposite, and more particularly, to a nanocomposite having a nanocomposite having a significantly increased surface area by growing a metal-organic structure on a substrate of a porous two-dimensional nanocomposite having active pores having a size of several tens of nanometers And a technology for applying it to a sensor, a catalyst, a separator, and the like.
금속-유기 구조체(metal organic frameworks, MOF)는 금속 이온 또는 금속 이온 클러스터가 유기 리간드와 배위결합을 통해 형성된 결정성 유무기 하이브리드 물질이다. 이러한 금속-유기 구조체는 다양한 작용기와 큰 표면적을 가지므로 센서, 촉매, 수소저장, 기체분리 등 많은 분야에 걸쳐 활발한 연구가 이루어지고 있다. 그러나 금속-유기 구조체 그 자체로는 결정성이 높아 가공성이 떨어지는바, 나노복합체를 구성하는 첨가제로서 주로 사용되는데, 고분자와 혼합되는 경우에는 유기체인 고분자와 무기체에 가까운 금속-유기 구조체 사이의 상호작용이 좋지 않아 응집 현상이 빈번히 발생함으로써 비활성화의 단점이 있다. 따라서 금속-유기 구조체의 특성을 발현하기 위해서는 매우 높은 농도가 필요한 실정이다.
Metal organic frameworks (MOF) are crystalline organic / inorganic hybrid materials in which metal ions or metal ion clusters are coordinated with organic ligands. Since these metal-organic structures have various functional groups and large surface area, they have been actively studied in many fields such as sensors, catalysts, hydrogen storage, and gas separation. However, the metal-organic structure itself has high crystallinity and poor processability. Therefore, it is mainly used as an additive constituting the nanocomposite. In the case of mixing with the polymer, the interaction between the organic polymer and the metal- Is not good, so that there is a disadvantage of inactivation due to occurrence of flocculation phenomenon frequently. Therefore, a very high concentration is required in order to manifest the characteristics of the metal-organic structure.
또한, 금속-유기 구조체의 특성을 개선하고 새로운 기능을 부여하기 위해 그래핀과 같은 2차원 나노소재와 융합하여 복합체를 제조하는 연구도 알려져 있는바, 일반적으로 금속-유기 구조체를 2차원 나노시트의 기재 상에 성장시켰을 때 종횡비가 증가하여 표면적이 높을 것이라 기대할 수 있지만, 성장 사이트가 적어 고밀도의 성장이 어렵고 기재 자체의 표면적은 금속-유기 구조체에 비하여 매우 작아 성장 이후의 표면적이 금속-유기 구조체 자체의 표면적보다도 작은 문제점이 있다.In addition, studies have been made to prepare composites by fusing with two-dimensional nanomaterials such as graphene in order to improve the properties of metal-organic structures and to impart new functions. Generally, metal- It is expected that the surface area will be increased due to an increase in aspect ratio when grown on a substrate. However, it is difficult to grow high density due to few growth sites and the surface area of the substrate itself is very small as compared with the metal- Is smaller than the surface area.
따라서 본 발명자는 그래핀 옥사이드 등의 2차원 나노소재와 금속-유기 구조체의 복합체를 제조하기 위하여 연구를 거듭한 결과, 먼저 2차원 나노소재를 간단한 산화 열수처리 공정에 의해 수십 나노미터 크기의 활성 기공을 갖는 다공성 기재로 만들고, 상기 다공성 2차원 나노소재의 기재 상에 금속-유기 구조체를 성장시키면, 금속-유기 구조체가 균일하게 고밀도로 성장함으로써 나노복합체의 표면적이 현저하게 향상됨을 발견하였고, 나아가 이렇게 얻어진 나노복합체는 고분자와 융합하여 기체분리용 복합막으로 응용할 수 있음에 착안하여 본 발명을 완성하기에 이르렀다.
Accordingly, the present inventors have conducted extensive research to produce a complex of a two-dimensional nanomaterial such as graphene oxide and a metal-organic structure. As a result, it has been found that a two-dimensional nanomaterial is first activated by a simple oxidative hydrothermal treatment process, And the surface of the nanocomposite is remarkably improved by growing the metal-organic structure uniformly at a high density when the metal-organic structure is grown on the substrate of the porous two-dimensional nanomaterial. Further, The present invention has been completed based on the fact that the obtained nanocomposite can be applied as a composite membrane for gas separation by fusion with a polymer.
본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 목적은 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재 상에 금속-유기 구조체를 성장시킴으로써 표면적이 현저하게 향상된 신규한 나노복합체 및 그 제조방법을 제공하고자 하는 것이다.
SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a porous two-dimensional nanomaterial having activated pores having a size of 10 to 40 nm, And to provide a novel nanocomposite and a manufacturing method thereof.
상기한 바와 같은 목적을 달성하기 위한 본 발명은, 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재; 및 상기 기재 상에 성장된 금속-유기 구조체;를 포함하는 나노복합체를 제공한다.To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described herein, there is provided a porous two-dimensional nanomaterial substrate having active pores having a size of 10 to 40 nm; And a metal-organic structure grown on the substrate.
상기 2차원 나노소재는 그래핀, 플루오로그래핀, 그래핀 옥사이드, 육방정계 질화붕소 및 붕소-질소-탄소(BCN) 화합물로 이루어진 군으로부터 선택된 어느 하나의 것을 특징으로 한다.Wherein the two-dimensional nanomaterial is characterized by any one selected from the group consisting of graphene, fluorographene, graphene oxide, hexagonal boron nitride and boron-nitrogen-carbon (BCN) compounds.
상기 2차원 나노소재는 2차원 칼코겐화합물, 2차원 산화물, 흑린(black phosphorus) 또는 포스포린인 것을 특징으로 한다.The two-dimensional nanomaterial is characterized by being a two-dimensional chalcogenide compound, a two-dimensional oxide, black phosphorus, or a phospholine.
상기 금속-유기 구조체는 제올라이트 이미다졸레이트 구조체인 것을 특징으로 한다.
Wherein the metal-organic structure is a zeolite imidazolate structure.
또한, 본 발명은 I) 2차원 나노소재를 준비하는 단계; II) 상기 2차원 나노소재를 산화열수처리 공정에 의하여 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재를 형성하는 단계; 및 III) 상기 기재 상에 용매 하에서 금속-유기 구조체를 성장시킨 후, 세척 및 건조하는 단계;를 포함하는 나노복합체의 제조방법을 제공한다.The present invention also provides a method of manufacturing a two-dimensional nanomaterial, comprising the steps of: I) preparing a two-dimensional nanomaterial; II) forming a porous two-dimensional nanomaterial substrate having active pores having a size of 10 to 40 nm by oxidative hydrothermal treatment of the two-dimensional nanomaterial; And III) growing a metal-organic structure on the substrate in a solvent, and then washing and drying the nanocomposite.
상기 2차원 나노소재는 그래핀, 플루오로그래핀, 그래핀 옥사이드, 육방정계 질화붕소 및 붕소-질소-탄소(BCN) 화합물로 이루어진 군으로부터 선택된 어느 하나의 것을 특징으로 한다.Wherein the two-dimensional nanomaterial is characterized by any one selected from the group consisting of graphene, fluorographene, graphene oxide, hexagonal boron nitride and boron-nitrogen-carbon (BCN) compounds.
상기 산화열수처리 공정은 2차원 나노소재를 산화제로 처리한 후, 고압반응기에서 150~200℃로 6~12시간 반응시키는 것을 특징으로 한다.The oxidation hydrothermal treatment process is characterized in that the two-dimensional nanomaterial is treated with an oxidizing agent and then reacted at 150 to 200 ° C for 6 to 12 hours in a high-pressure reactor.
상기 산화제는 과산화수소인 것을 특징으로 한다.The oxidizing agent is characterized by being hydrogen peroxide.
상기 용매는 메탄올, 에탄올, 증류수 또는 이소프로판올인 것을 특징으로 한다.
Wherein the solvent is methanol, ethanol, distilled water or isopropanol.
또한, 본 발명은 상기 나노복합체를 포함하는 기체분리용 고분자 복합막을 제공한다.The present invention also provides a polymer composite membrane for gas separation comprising the nanocomposite.
상기 기체는 CO2/N2의 혼합기체인 것을 특징으로 한다.
The gas is characterized by being a mixed gas of CO 2 / N 2 .
본 발명에 따라 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재 상에 금속-유기 구조체가 균일하게 고밀도로 성장된 나노복합체는 표면적이 현저하게 향상됨으로써 종래에 비하여 적은 함량으로도 센서, 촉매 및 분리막 등에 응용이 가능하다.
According to the present invention, a nanocomposite in which a metal-organic structure is uniformly and densely grown on a substrate of a porous two-dimensional nanomaterial having active pores having a size of 10 to 40 nm is remarkably improved in surface area, Sensors, catalysts and membranes.
도 1은 본 발명의 실시예 1에 따른 2차원 나노소재로서 그래핀 옥사이드의 투과전자현미경(TEM) 이미지.
도 2는 본 발명의 실시예 1에 따라 형성된 다공성 그래핀 옥사이드의 투과전자현미경(TEM) 이미지.
도 3은 본 발명의 실시예 1에 따라 다공성 그래핀 옥사이드 기재 상에 성장된 아연-이미다졸 구조체로 이루어진 나노복합체의 투과전자현미경(TEM) 이미지.
도 4는 본 발명의 실시예 1로부터 제조된 나노복합체(아연-이미다졸 구조체/다공성 그래핀 옥사이드) 분말의 주사전자현미경(SEM) 이미지.
도 5는 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite) 분말의 X-선 회절(XRD) 패턴을 나타낸 그래프.
도 6은 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite)의 BET 기공분포를 나타낸 그래프.
도 7은 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite)의 X-선 광전자분석(XPS) 결과를 나타낸 그래프.
도 8은 본 발명의 실시예 1로부터 제조된 나노복합체(Composite)의 열중량분석(TGA) 결과를 나타낸 그래프.
도 9는 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite)의 BET 등온곡선을 나타낸 그래프.
도 10은 본 발명의 실시예 2로부터 제조된 고분자 복합막(+composite)과 실시예 1에 따른 아연-이미다졸 구조체를 상용화 Pebax-1657 분리막에 혼합한 고분자 복합막(+MOF) 및 상용화 Pebax-1657 분리막 자체(Neat Polymer)의 CO2/N2 분리 특성을 나타낸 그래프.
도 11은 본 발명의 실시예 2로부터 제조된 고분자 복합막(+composite)과 상용화 Pebax-1657 분리막 자체(Neat Polymer)의 압력증가에 따른 CO2/N2 혼합기체의 선택도 변화를 나타낸 그래프.
1 is a transmission electron microscope (TEM) image of graphene oxide as a two-dimensional nanomaterial according to Example 1 of the present invention.
2 is a transmission electron microscope (TEM) image of porous graphene oxide formed according to Example 1 of the present invention.
3 is a transmission electron microscopy (TEM) image of a nanocomposite composed of a zinc-imidazole structure grown on a porous graphene oxide substrate according to Example 1 of the present invention.
4 is a scanning electron microscope (SEM) image of the nanocomposite (zinc-imidazole structure / porous graphene oxide) powder prepared from Example 1 of the present invention.
5 is a graph showing an X-ray diffraction (XRD) pattern of a zinc-imidazole structure (MOF) and a nanocomposite powder according to Example 1 of the present invention.
6 is a graph showing BET pore distribution of a zinc-imidazole structure (MOF) and a nanocomposite according to Example 1 of the present invention.
7 is a graph showing X-ray photoelectron spectroscopic (XPS) results of a zinc-imidazole structure (MOF) and a nanocomposite composite according to Example 1 of the present invention.
8 is a graph showing a result of thermogravimetric analysis (TGA) of a nanocomposite composite prepared from Example 1 of the present invention.
9 is a graph showing the BET isotherm curves of a zinc-imidazole structure (MOF) and a nanocomposite according to Example 1 of the present invention.
10 is a view showing a polymer composite membrane (+ MOF) obtained by mixing a polymer composite membrane (+ composite) prepared in Example 2 of the present invention and a zinc-imidazole structure according to Example 1 in a commercial Pebax-1657 membrane, and a commercialized Pebax- 1657 A graph showing the CO 2 / N 2 separation characteristics of the membrane itself (Neat Polymer).
11 is a graph showing changes in selectivity of CO 2 / N 2 mixed gas due to an increase in pressure of the polymer composite membrane (+ composite) prepared in Example 2 of the present invention and the commercialized Pebax-1657 membrane itself (Neat Polymer).
이하에서는 본 발명에 따른 신규한 나노복합체 및 그 제조방법에 관하여 상세히 설명하기로 한다.Hereinafter, a novel nanocomposite according to the present invention and a method for producing the same will be described in detail.
본 발명에는 종래 금속-유기 구조체를 통상의 2차원 나노시트의 기재 상에 성장시키는 과정에서 성장 사이트가 적어 고밀도의 성장이 어렵고 기재 자체의 표면적이 금속-유기 구조체에 비하여 매우 작아 성장 이후의 표면적이 금속-유기 구조체 자체의 표면적보다도 작은 문제점을 해결하기 위하여, 먼저 2차원 나노소재를 간단한 산화 열수처리 공정에 의해 수십 나노미터 크기의 활성 기공을 갖는 다공성 기재로 만들고, 이어서 상기 다공성 2차원 나노소재의 기재 상에 금속-유기 구조체를 성장시키면, 금속-유기 구조체가 균일하게 고밀도로 성장함으로써 나노복합체의 표면적이 현저하게 향상됨을 발견한 기술적 사상이 내재되어 있다.In the present invention, since the conventional metal-organic structure is grown on a substrate of a conventional two-dimensional nanosheet, it is difficult to grow at a high density due to few growth sites, and the surface area of the substrate itself is very small as compared with the metal- In order to solve the problem that the surface area of the metal-organic structure itself is smaller than the surface area of the metal-organic structure itself, a two-dimensional nanomaterial is first made into a porous substrate having active pores having a size of several tens of nanometers by a simple oxidation hydrothermal treatment process, It has been found that when the metal-organic structure is grown on a substrate, the surface area of the nanocomposite is remarkably improved by growing the metal-organic structure uniformly at a high density.
따라서 본 발명은 10~40 nm 크기의 기공을 갖는 다공성 2차원 나노소재의 기재; 및 상기 기재 상에 성장된 금속-유기 구조체;를 포함하는 나노복합체를 제공한다.Accordingly, the present invention provides a porous two-dimensional nanomaterial substrate having a pore size of 10 to 40 nm; And a metal-organic structure grown on the substrate.
먼저, 본 발명에서는 층상구조를 이루는 2차원 나노소재로서 그래핀 계열의 물질을 사용할 수 있는바, 그래핀, 플루오로그래핀, 그래핀 옥사이드, 육방정계 질화붕소(hexagonal boron nitride, h-BN) 및 붕소-질소-탄소(BCN) 화합물로 이루어진 군으로부터 선택된 어느 하나의 것을 바람직하게 사용하며, 특히 최근에 촉매, 센서, 분리막 등 다양한 분야에 응용연구가 활발히 수행되고 있는 그래핀 옥사이드를 더욱 바람직하게 사용한다.In the present invention, a graphene-based material can be used as a two-dimensional nano material forming a layered structure, and graphene, fluorographene, graphene oxide, hexagonal boron nitride (h-BN) And a boron-nitrogen-carbon (BCN) compound. Particularly, graphene oxide, which has been actively applied in various fields such as catalysts, sensors and separators, is more preferably used use.
또한, 2차원 나노소재로서는 상기 그래핀 계열의 물질 이외에 2차원 칼코겐화합물, 2차원 산화물, 흑린(black phosphorus) 또는 포스포린(phosphorene)도 가능하다. 2차원 칼코겐화합물로는 보통 전이금속 칼코겐 화합물(transition metal dichalcogenide, TMD)로 불리는 MX2(M=전이금속, X=칼코겐원소)로서 MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, ZrS2, ZrSe2 둥이 있으며, 또한 전이금속 칼코겐 화합물(transition metal trichalcogenide, TMT)로 불리는 MX3로서 TiS3, TiSe3, ZrS3, ZrSe3 등이 있다.As the two-dimensional nanomaterial, a two-dimensional chalcogenide compound, a two-dimensional oxide, a black phosphorus, or a phosphorane may be used in addition to the graphene-based material. As the two-dimensional chalcogen compound, MX 2 (M = transition metal, X = chalcogen element), which is usually referred to as a transition metal dichalcogenide (TMD), MoS 2 , WS 2 , MoSe 2 , WSe 2 , MoTe 2, snout and WTe 2, ZrS 2, ZrSe 2, also referred to as MX 3 with a transition metal chalcogen compound (transition metal trichalcogenide, TMT) include TiS 3, TiSe 3, ZrS 3 , ZrSe 3.
또한, 상기 2차원 산화물로는 MoO3, WO3, TiO2, MnO2, V2O5, TaO3, RuO2 등을 예로 들 수 있다.
Examples of the two-dimensional oxide include MoO 3 , WO 3 , TiO 2 , MnO 2 , V 2 O 5 , TaO 3 and RuO 2 .
한편, 본 발명에 따른 신규한 나노복합체의 일 성분으로서 금속-유기 구조체(metal organic frameworks, MOF)는 금속 이온 또는 금속 이온 클러스터가 유기 리간드와 배위결합을 통해 형성된 결정성 유무기 하이브리드 물질이다. 이때, 상기 금속-유기 구조체로서는 공지된 다양한 물질을 제한 없이 사용할 수 있는데, 특히 MOF 부류 중에서도 높은 열적·화학적 안정성을 가진 것으로 알려진 제올라이트 이미다졸레이트 구조체(zeolitic imidazolate framework, ZIF) 계열의 아연-이미다졸 구조체를 바람직하게 사용한다.
Meanwhile, metal organic frameworks (MOF) as one component of the novel nanocomposite according to the present invention are crystalline organic or inorganic hybrid materials formed by coordination of metal ions or metal ion clusters with organic ligands. As the metal-organic structure, various known materials can be used without limitation. In particular, zeolitic imidazolate framework (ZIF) -based zinc-imidazole (ZIF) series, which is known to have high thermal / Structures are preferably used.
또한, 본 발명에서는 상술한 나노복합체를 얻기 위하여 I) 2차원 나노소재를 준비하는 단계; II) 상기 2차원 나노소재를 산화열수처리 공정에 의하여 10~40 nm 크기의 기공을 갖는 다공성 2차원 나노소재의 기재를 형성하는 단계; 및 III) 상기 기재 상에 용매 하에서 금속-유기 구조체를 성장시킨 후, 세척 및 건조하는 단계;를 포함하는 나노복합체의 제조방법을 제공한다.In addition, in the present invention, in order to obtain the above-described nanocomposite, a step of preparing I) a two-dimensional nanomaterial; II) forming a porous two-dimensional nanomaterial substrate having pores having a size of 10 to 40 nm by an oxidative hydrothermal treatment process of the two-dimensional nanomaterial; And III) growing a metal-organic structure on the substrate in a solvent, and then washing and drying the nanocomposite.
상기 2차원 나노소재로서는 상술한 바와 같이 그래핀, 플루오로그래핀, 그래핀 옥사이드, 육방정계 질화붕소 및 붕소-질소-탄소(BCN) 화합물로 이루어진 군으로부터 선택된 어느 하나의 것을 바람직하게 사용하며, 그래핀 옥사이드를 더욱 바람직하게 사용한다.As the two-dimensional nanomaterial, any one selected from the group consisting of graphene, fluorographene, graphene oxide, hexagonal boron nitride and boron-nitrogen-carbon (BCN) compounds is preferably used, Graphenoxide is more preferably used.
상기 II) 단계에서는 2차원 나노소재를 대상으로 간단한 산화열수처리 공정을 수행하는바, 2차원 나노소재를 과산화수소와 같은 산화제로 처리한 후, 고압반응기에서 150~200℃로 6~12시간 반응을 수행함으로써 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재를 형성한다.In the step II), a simple oxidative hydrothermal treatment process is performed on a two-dimensional nanomaterial. After the two-dimensional nanomaterial is treated with an oxidizing agent such as hydrogen peroxide, the reaction is carried out at 150 to 200 ° C for 6 to 12 hours in a high- To form a porous two-dimensional nanomaterial substrate having active pores of 10 to 40 nm in size.
이어서 상기 III) 단계에서는 II) 단계로부터 얻어진 수십 나노미터 크기의 기공을 갖는 다공성 2차원 나노소재의 기재 상에 용매 하에서 금속-유기 구조체를 성장시킨 후, 세척 및 건조함으로써 나노복합체를 제조한다. 이때, 금속-유기 구조체로서는 상술한 바와 같이 제올라이트 이미다졸레이트 구조체(zeolitic imidazolate framework, ZIF) 계열의 아연-이미다졸 구조체를 바람직하게 사용하며, 용매로서는 메탄올, 에탄올, 증류수 또는 이소프로판올을 더욱 바람직하게 사용한다.
Next, in step III), a metal-organic structure is grown on a substrate of porous two-dimensional nanomaterial having pores of several tens of nanometers in size obtained from step II), washed, and dried to prepare a nanocomposite. As the metal-organic structure, a zinc-imidazole structure based on a zeolite imidazolate framework (ZIF) is preferably used. As the solvent, methanol, ethanol, distilled water or isopropanol is more preferably used do.
상술한 제조방법의 I) 내지 III) 단계 중 II) 단계 공정으로 인하여 통상적인 2차원 나노소재에 10~40 nm 크기의 활성 기공을 형성할 수 있으며, 이렇게 얻어진 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재를 기재로 하여 그 기재 상에 금속-유기 구조체를 균일하게 고밀도로 성장시킨 나노복합체를 얻을 수 있다.
Due to the process steps II) to III) of the above-mentioned production method, active pores having a size of 10 to 40 nm can be formed on a conventional two-dimensional nanomaterial, and the obtained activated pores having a size of 10 to 40 nm A nanocomposite can be obtained in which a metal-organic structure is uniformly grown at a high density on a base material of a porous two-dimensional nanomaterial having the above-mentioned structure.
또한, 본 발명에서는 상기 나노복합체를 포함하는 기체분리용 고분자 복합막을 제공하는바, 공지의 방법에 따라 상기 나노복합체를 함유하는 복합막을 제조하여 다양한 혼합기체로부터 특정의 기체를 선택적으로 분리할 수 있는 기체분리막으로 응용할 수 있으며, 특히 종래 상용막(Pebax-1657)에 비하여 이산화탄소의 투과도가 크게 향상되면서도 질소에 대한 이산화탄소의 선택도 또한 소폭 향상되어 CO2/N2의 혼합기체로부터 이산화탄소를 선택적으로 분리하는데 유용하다.In addition, the present invention provides a polymer composite membrane for gas separation comprising the nanocomposite, wherein a composite membrane containing the nanocomposite is prepared according to a known method, and a specific gas can be selectively separated from various mixed gases Gas separation membrane. Particularly, the permeability of carbon dioxide is greatly improved compared to the conventional membrane (Pebax-1657), and the selection of carbon dioxide for nitrogen is also slightly improved, thereby selectively separating carbon dioxide from the mixed gas of CO 2 / N 2 .
이하 구체적인 실시예를 첨부된 도면과 함께 상세히 설명한다.
Hereinafter, specific embodiments will be described in detail with reference to the accompanying drawings.
(실시예 1) 아연-이미다졸 구조체/다공성 그래핀 옥사이드 나노복합체의 제조(Example 1) Preparation of zinc-imidazole structure / porous graphene oxide nanocomposite
그래핀 옥사이드(도 1 참조) 0.1 중량% 수용액에 과산화수소를 산화제로 사용하여 10분간 소니케이션 한 후, 고압반응기(오토클레이브)에서 180℃로 6시간 열수반응시켜 10~40 nm 크기의 활성 기공을 갖는 다공성 그래핀 옥사이드를 형성하였다. 상기 형성된 다공성 그래핀 옥사이드 상에 메탄올 하에서 MOF인 아연-이미다졸 구조체(ZIF-8)를 5시간에 걸쳐 성장시키고, 메탄올로 3회 세척 및 건조하여 아연-이미다졸 구조체/다공성 그래핀 옥사이드 나노복합체(Composite)를 제조하였다.
Hydrogen peroxide was sonicated for 10 minutes in 0.1 wt% aqueous solution of graphene oxide (see FIG. 1) as an oxidizing agent, and then subjected to hot water reaction at 180 ° C. for 6 hours in a high pressure reactor (autoclave) to form active pores having a size of 10 to 40 nm To form porous graphene oxide. A zinc-imidazole structure (ZIF-8), which is a MOF under methanol, was grown on the formed porous graphene oxide over 5 hours, washed three times with methanol and dried to obtain a zinc-imidazole structure / porous graphene oxide nanocomposite (Composite).
(실시예 2) 나노복합체를 함유하는 고분자 복합막의 제조(Example 2) Production of a polymer composite membrane containing a nanocomposite
상기 실시예 1로부터 제조된 나노복합체를 에탄올과 물의 혼합용매(7:3 부피비) 하에서 상용막인 Pebax-1657에 혼합하여 증발 방식으로 고분자 복합막을 제조하였으며(고분자 복합막 내 나노복합체의 농도는 4~6 μg/mL), 이를 이용하여 기체(CO2/N2) 분리 특성을 시험하였다.
The nanocomposite prepared in Example 1 was mixed with a commercial membrane Pebax-1657 in a mixed solvent of ethanol and water (7: 3 volume ratio) to prepare a polymer composite membrane by evaporation (the concentration of the nanocomposite in the polymer composite membrane was 4 ~ 6 μg / mL), and the gas (CO 2 / N 2 ) separation characteristics were tested using this.
도 1에는 본 발명의 실시예 1에 따른 2차원 나노소재로서 그래핀 옥사이드의 투과전자현미경(TEM) 이미지를, 또한 도 2에는 본 발명의 실시예 1에 따라 형성된 다공성 그래핀 옥사이드의 투과전자현미경(TEM) 이미지를 나타내었는바, 도 2로부터 2차원 나노소재인 그래핀 옥사이드가 간단한 산화열수처리 공정에 의하여 수십 나노미터 크기의 기공을 갖는 다공성으로 전환되었음을 확인할 수 있다.
FIG. 1 shows a transmission electron microscope (TEM) image of graphene oxide as a two-dimensional nanomaterial according to Example 1 of the present invention, and FIG. 2 also shows a transmission electron microscope (TEM) image of a porous graphene oxide formed according to Example 1 of the present invention (TEM) image. From FIG. 2, it can be seen that graphene oxide, which is a two-dimensional nanomaterial, has been converted into porosity having a pore size of several tens of nanometers by a simple oxidation hydrothermal treatment process.
도 3 및 4에는 각각 본 발명의 실시예 1에 따라 다공성 그래핀 옥사이드 기재 상에 성장된 아연-이미다졸 구조체로 이루어진 나노복합체의 투과전자현미경(TEM) 이미지 및 본 발명의 실시예 1로부터 제조된 나노복합체(아연-이미다졸 구조체/다공성 그래핀 옥사이드) 분말의 주사전자현미경(SEM) 이미지를 나타내었는바, 다공성 그래핀 옥사이드 기재 상에 아연-이미다졸 구조체가 성장한 이후에도 2차원 평면 구조를 유지하는 것을 확인할 수 있다.
FIGS. 3 and 4 show transmission electron microscope (TEM) images of nanocomposites composed of zinc-imidazole structures grown on a porous graphene oxide substrate according to Example 1 of the present invention, respectively, The SEM image of the nanocomposite (zinc-imidazole structure / porous graphene oxide) powder is shown, which shows that after the zinc-imidazole structure is grown on the porous graphene oxide substrate, .
또한, 도 5 및 6에는 각각 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite) 분말의 X-선 회절(XRD) 패턴 및 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite)의 BET 기공분포를 나타내었는바, 아연-이미다졸 구조체가 다공성 그래핀 옥사이드 기재 상에 균일하게 고밀도로 성장하였음을 알 수 있다.
5 and 6 show X-ray diffraction patterns (XRD) patterns of zinc-imidazole structure (MOF) and nanocomposite powder according to Example 1 of the present invention and zinc -Imidazole structure (MOF) and nanocomposite (Composite), it can be seen that the zinc-imidazole structure was uniformly grown at high density on the porous graphene oxide substrate.
도 7에 나타낸 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite)의 X-선 광전자분석(XPS) 결과 그래프로부터는 다공성 그래핀 옥사이드 기재와 아연-이미다졸 구조체 사이에 새로운 화학적 작용이 존재하는 것을 알 수 있다.
X-ray photoelectron spectroscopy (XPS) results of the zinc-imidazole structure (MOF) and the nanocomposite composite according to Example 1 of the present invention shown in FIG. 7 show that the porous graphene oxide base and the zinc- It can be seen that there is a new chemical action between them.
또한, 도 8에 나타낸 바와 같이, 본 발명의 실시예 1로부터 제조된 나노복합체(Composite)의 열중량분석(TGA) 결과로부터는 나노복합체 내에서 다공성 그래핀 옥사이드 기재와 아연-이미다졸 구조체의 중량비 및 그에 따른 열적 안정성을 확인할 수 있다.
As shown in FIG. 8, from the thermogravimetric analysis (TGA) results of the nanocomposite prepared from Example 1 of the present invention, the weight ratio of the porous graphene oxide base material and the zinc-imidazole structure in the nanocomposite And its thermal stability can be confirmed.
아울러 도 9에는 본 발명의 실시예 1에 따른 아연-이미다졸 구조체(MOF) 및 나노복합체(Composite)의 BET 등온곡선을 나타내었는바, BET 등온곡선으로부터 아연-이미다졸 구조체(MOF)와 나노복합체(Composite) 각각의 표면적을 계산한 결과, 아연-이미다졸 구조체(MOF)는 1720 m2/g, 나노복합체(Composite)는 2170 m2/g으로서 나노복합체(Composite)가 아연-이미다졸 구조체(MOF)에 비하여 약 26% 정도 BET 표면적이 증가하였음을 알았다. 이러한 BET 표면적의 값은 종래 보고된 나노복합체의 BET 표면적[HF 그래핀 옥사이드/ZIF-8 : 590 m2/g, 그래핀 옥사이드/ZIF-8 : 819 m2/g, 환원된 그래핀 옥사이드/ZIF-8 : 720 m2/g]에 비하여도 현저하게 높다.
9 shows the BET isotherm curves of the zinc-imidazole structure (MOF) and the nanocomposite according to Example 1 of the present invention. From the BET isotherm curve, the zinc-imidazole structure (MOF) and the nanocomposite (MOF) of 1720 m 2 / g and a composite of 2170 m 2 / g as a result of the calculation of the surface area of each of the zinc-imidazole structure (composite) and the zinc-imidazole structure MOF), the BET surface area increased by about 26%. The value of this BET surface area was calculated from the BET surface area of conventional nanocomposites (HF graphene oxide / ZIF-8: 590 m 2 / g, graphene oxide / ZIF-8: 819 m 2 / g, reduced graphene oxide / ZIF-8: 720 m 2 / g].
한편, 도 10에는 본 발명의 실시예 2로부터 제조된 고분자 복합막(+composite)과 실시예 1에 따른 아연-이미다졸 구조체를 상용화 Pebax-1657 분리막에 혼합한 고분자 복합막(+MOF) 및 상용화 Pebax-1657 분리막 자체(Neat Polymer)의 CO2/N2 분리 특성을 그래프로 나타내었는바, 실시예 2로부터 제조된 고분자 복합막(+composite)은 실시예 1에 따른 아연-이미다졸 구조체를 상용화 Pebax-1657 분리막에 혼합한 고분자 복합막(+MOF) 및 상용화 Pebax-1657 분리막 자체(Neat Polymer)에 비하여 질소에 대한 이산화탄소의 선택도가 유지되면서도 이산화탄소의 투과도가 크게 증가함을 알 수 있다.
10 shows a polymer composite membrane (+ MOF) obtained by mixing the polymer composite membrane (+ composite) prepared in Example 2 of the present invention and the zinc-imidazole structure according to Example 1 in a commercial Pebax-1657 membrane, The CO 2 / N 2 separation characteristics of the Pebax-1657 membrane itself (Neat Polymer) were graphically shown. The polymer composite membrane (+ composite) prepared in Example 2 was prepared by commercializing the zinc-imidazole structure according to Example 1 It can be seen that the permeability of carbon dioxide is greatly increased while maintaining the selectivity of carbon dioxide for nitrogen compared with the polymer composite membrane (+ MOF) mixed with Pebax-1657 membrane and the commercialized Pebax-1657 membrane itself (Neat Polymer).
또한, 도 11에는 본 발명의 실시예 2로부터 제조된 고분자 복합막(+composite)과 상용화 Pebax-1657 분리막 자체(Neat Polymer)의 압력증가에 따른 CO2/N2 혼합기체의 선택도 변화를 그래프로 나타내었는바, 도 11로부터는 CO2/N2 혼합기체에서 압력을 올림에 따라 선택도가 떨어지고 투과도는 증가하는 가소화반응이 상용막에 비하여 본 발명의 실시예 2로부터 제조된 고분자 복합막(+composite)에서 현저하게 감소하는 것을 확인할 수 있다.
11 shows the change in the selectivity of the CO 2 / N 2 mixed gas with increasing pressure of the polymer composite membrane (+ composite) and the commercial Pebax-1657 membrane (Neat Polymer) prepared in Example 2 of the present invention 11 shows that the plasticizing reaction in which the selectivity is decreased and the permeability is increased as the pressure is raised in the CO 2 / N 2 mixed gas is higher than that of the polymer membrane prepared in Example 2 of the present invention (+ composite).
그러므로 본 발명에 따라 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재 상에 금속-유기 구조체가 균일하게 고밀도로 성장된 나노복합체는 표면적이 현저하게 향상됨으로써 종래에 비하여 적은 함량으로도 센서, 촉매 및 분리막 등에 응용이 가능하다.Therefore, according to the present invention, a nanocomposite having uniformly high density of metal-organic structures grown on a substrate of porous two-dimensional nanomaterial having active pores having a size of 10 to 40 nm has remarkably improved surface area, It can be applied to sensors, catalysts and membranes.
Claims (11)
상기 기재 상에 성장된 금속-유기 구조체;를 포함하는 나노복합체.A substrate of a porous two-dimensional nanomaterial having an active pore size of 10 to 40 nm; And
A nanocomposite comprising a metal-organic structure grown on the substrate.
II) 상기 2차원 나노소재를 산화열수처리 공정에 의하여 10~40 nm 크기의 활성 기공을 갖는 다공성 2차원 나노소재의 기재를 형성하는 단계; 및
III) 상기 기재 상에 용매 하에서 금속-유기 구조체를 성장시킨 후, 세척 및 건조하는 단계;를 포함하는 나노복합체의 제조방법.I) preparing a two-dimensional nanomaterial;
II) forming a porous two-dimensional nanomaterial substrate having active pores having a size of 10 to 40 nm by oxidative hydrothermal treatment of the two-dimensional nanomaterial; And
III) growing a metal-organic structure on the substrate in a solvent, and then washing and drying the nanocomposite.
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