KR20200049966A - Hybrid Nanomaterials containing dendritic fibrous nanosilica core - Zn-based coordination polymers shell or dendritic fibrous nanosilica/Au core - Zn-based coordination polymers shell, a synthetic method thereof and applications of the nanomaterials - Google Patents
Hybrid Nanomaterials containing dendritic fibrous nanosilica core - Zn-based coordination polymers shell or dendritic fibrous nanosilica/Au core - Zn-based coordination polymers shell, a synthetic method thereof and applications of the nanomaterials Download PDFInfo
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- KR20200049966A KR20200049966A KR1020180130450A KR20180130450A KR20200049966A KR 20200049966 A KR20200049966 A KR 20200049966A KR 1020180130450 A KR1020180130450 A KR 1020180130450A KR 20180130450 A KR20180130450 A KR 20180130450A KR 20200049966 A KR20200049966 A KR 20200049966A
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- nanosilica
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 57
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 57
- 239000002086 nanomaterial Substances 0.000 title abstract description 13
- 238000010189 synthetic method Methods 0.000 title description 2
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- 239000010931 gold Substances 0.000 claims abstract description 125
- 229910052737 gold Inorganic materials 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 39
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 33
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- 238000000034 method Methods 0.000 claims description 26
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 17
- 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 claims description 17
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- 125000003277 amino group Chemical group 0.000 description 5
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- 238000003917 TEM image Methods 0.000 description 3
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- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 3
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- 230000037303 wrinkles Effects 0.000 description 3
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- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 3
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 2
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- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 239000004809 Teflon Substances 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 239000012299 nitrogen atmosphere Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
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Images
Classifications
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- B01J35/19—
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/0006—Catalysts containing parts with different compositions
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/02—Solids
- B01J35/023—Catalysts characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/02—Solids
- B01J35/06—Fabrics or filaments
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- B01J35/40—
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- B01J35/58—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
Abstract
Description
본 발명은 돌기 섬유질형 나노실리카 코어와 Zn 기반 배위 고분자 쉘을 포함하는 나노입자, 혹은 돌기 섬유질형 나노실리카와 금 나노입자 코어와 Zn 기반 배위 고분자 쉘을 포함하는 혼성형 나노입자, 이의 생산방법과 이 나노입자들의 응용에 관한 것이다.The present invention relates to nanoparticles comprising a protruding fibrous nanosilica core and a Zn-based coordinating polymer shell, or hybrid nanoparticles comprising a protruding fibrous nanosilica and gold nanoparticle core and a Zn-based coordinating polymer shell, and a method for producing the same. It relates to the application of these nanoparticles.
최근에 많은 가지와 기공을 지닌 실리카 나노입자{본 발명에서는 돌기형의 넓은 표면을 보인다는 점을 강조하기 위해 돌기 섬유질형 나노실리카(Dendritic Fibrous Nanosilica, "DFNS") 라는 명칭을 사용함}가 보고된바 있다(1). 이 실리카 나노 입자는 높은 표면적 섬유질 표면의 형태를 보이며 특히 고온, 고압에서 높은 안정성을 나타낸다(1,2). 이 실리카 나노입자의 표면에 존재하는 하이드록시기(-OH)를 비교적 간단한 공정을 통해 다른 작용기로 변화시키는 표면 개질 단계를 진행하여 금(Au)이나 팔라듐(Pd), 백금(Pt), 루세늄 (Ru)이온 등을 표면에서만 선택적으로 환원하여 코어-쉘 나노입자를 합성한 연구결과가 보고되었다(3,4,5,6). 특히 금(Au) 입자나 금(Au) 레이어를 표면적이 큰 실리카 나노입자의 표면에 형성하는 예가 보고되었다. 일반적으로 다중 가지의 실리카 표면에 Au 나노입자들이 결합해 있는 구조를 보인다(3). 또한, 표면의 Au 나노입자의 크기나 수를 조절하기 위해서는 사용하는 Au 이온의 양을 증가시키거나 환원제의 양을 조절하는 것이 일반적이다. 또한, 시드 매개법(seed mediated growth method)을 도입하여 많은 가지와 기공을 지닌 실리카 표면에서 금을 성장시키는 방식으로 표면을 Au 나노입자 구조체로 완전히 둘러싼 구조체를 포함하여, 혼성물질의 구조를 조절할 수 있다(7).Recently, silica nanoparticles having many branches and pores (in the present invention, the term "Dendritic Fibrous Nanosilica" (DFNS)) is used to emphasize the fact that it exhibits a large surface of a protrusion) has been reported. There is a bar (1). The silica nanoparticles have a high surface area, a fibrous surface, and particularly high temperature and high pressure stability (1,2). The surface modification step of converting the hydroxy group (-OH) present on the surface of the silica nanoparticles to another functional group through a relatively simple process is performed to perform gold (Au), palladium (Pd), platinum (Pt), and ruthenium. Research results have been reported on the synthesis of core-shell nanoparticles by selectively reducing (Ru) ions and the like only on the surface (3,4,5,6). In particular, an example of forming a gold (Au) particle or a gold (Au) layer on the surface of a silica nanoparticle having a large surface area has been reported. In general, it shows a structure in which Au nanoparticles are bonded to multiple types of silica surfaces (3). In addition, in order to control the size or number of Au nanoparticles on the surface, it is common to increase the amount of Au ions used or to control the amount of reducing agent. In addition, by introducing a seed mediated growth method, a method of growing gold on a silica surface having many branches and pores, including a structure completely surrounding the surface with an Au nanoparticle structure, to control the structure of the hybrid material. Yes (7).
삼차원 배위 고분자 입자는 통상 금속 이온 또는 클러스터와 다중토픽 유기 링커 (multitopic organic linkers)의 배위-기반 조립을 통해 형성되며, 높은 다공성, 명확히 한정된 공극 크기 및 구조적인 맞춤 가능성 등의 특징을 나타낸다(8). 특히, 나노구조 배위 고분자 입자는 크기-, 모양- 및 구성요소-의존적 특성으로 인하여 많은 관심의 대상이 되고 있다(9). 특히 아연(Zn) 기반의 금속-유기 구조체(Metal-Organic Framework, MOF)나 배위 고분자 입자는 다공성이 높고 다기능을 가지며, 나노구조 배위 고분자 입자를 형성할 경우 독특한 크기와 형태를 지닐 수 있어 관심을 끈다(10). Zn 기반 배위 고분자 나노큐브 제조시 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 {2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가해 제조하면, 이 리간드가 나노구조 배위 고분자의 크기와 형상을 제어하는 효과적인 형상 지시 조절인자(shape-directing modulator)로 이용될 수 있다(11). 또한, [N3] 리간드가 구리 이온과 같은 다른 기능성 금속의 장식에 적합한 금속결합부위를 제공할 수 있으므로 배위 고분자 자체를 유용한 촉매로 이용할 수 있다.Three-dimensional coordination polymer particles are usually formed through coordination-based assembly of metal ions or clusters and multitopic organic linkers, and exhibit characteristics such as high porosity, clearly defined pore size and structural fitability (8) . In particular, nanostructured coordination polymer particles are of great interest due to their size-, shape- and component-dependent properties (9). Particularly, zinc-based metal-organic frameworks (MOFs) or coordination polymer particles have high porosity and multifunctionality, and when forming nanostructure coordination polymer particles, they can have a unique size and shape, which is of interest. Turn off (10). When the Zn-based coordination polymer nanocube is prepared, 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine {2,6-bis [(4-carboxyanilino) carbonyl] pyridine} ligand is added to prepare this ligand. It can be used as an effective shape-directing modulator that controls the size and shape of the nanostructured coordination polymer (11). In addition, since the [N3] ligand can provide a metal bonding site suitable for decoration of other functional metals such as copper ions, the coordination polymer itself can be used as a useful catalyst.
이와 같이 독특한 구조적 특성을 지니는 돌기 섬유질형 나노실리카와 배위 고분자의 혼성체는 아직 보고되지 않았다. 더구나 돌기 섬유질형 나노실리카와 금 나노입자, 그리고 배위 고분자가 혼성되어 있는 구조체는 합성예가 없다. 이러한 구조체는 표면적이 넓은 실리카의 구조적 성질을 이용할 수 있으며 특히 나노실리카와 배위 고분자 사이의 빈 공간을 나노 크기의 반응용기나 물질저장, 수송 등의 용도로 활용할 수 있다. 금과 같이 촉매기능이 우수한 금속성 나노입자는 상대적으로 안정성이 떨어지지만 표면적이 넓은 나노실리카를 지지체로 이용하면서 외곽의 배위 고분자에 의해 보호될 수 있으므로 안정성을 비약적으로 높일 수 있다. 아울러, 배위 고분자의 다공성은 물질의 선택적 출입을 용이하게 할 수 있다. 특히 Zn-기반의 배위 고분자는 다공성이나 구조적 성질이 우수하고, [N3] 리간드를 도입할 경우 추가로 금속이온을 배위시킬 수 있어 다기능성 나노구조체 형성이 가능하다.A hybrid of a protruding fibrous nanosilica and a coordinating polymer having such unique structural properties has not been reported. Moreover, there is no synthetic example of a structure in which protruding fibrous nanosilica, gold nanoparticles, and coordination polymer are mixed. Such a structure can utilize the structural properties of silica having a large surface area, and in particular, an empty space between nano-silica and a coordinating polymer can be used for a nano-sized reaction vessel, material storage, and transportation. Metallic nanoparticles having excellent catalytic functions, such as gold, have relatively poor stability, but can be protected by an outer coordination polymer while using nano-silica with a large surface area as a support, so that stability can be dramatically improved. In addition, the porosity of the coordination polymer can facilitate selective entry and exit of the material. In particular, the Zn-based coordination polymer has excellent porosity or structural properties, and when introducing the [N3] ligand, metal ions can be additionally coordinated to form a multifunctional nanostructure.
본 발명은 좀 더 효과적인 실리카 코어 배위 고분자 쉘 구조의 나노입자와 실리카 코어 금 나노입자/배위 고분자 쉘 구조의 혼성형 나노입자, 그 합성방법 및 응용방법을 제공하는 것을 과제로 한다.The present invention aims to provide more effective silica core coordination polymer shell structure nanoparticles and silica core gold nanoparticles / coordination polymer shell structure hybrid nanoparticles, synthetic methods and application methods thereof.
본 발명에서는 많은 가지와 기공을 지닌 실리카 나노입자(본 발명에서는 돌기형의 넓은 표면을 보인다는 점을 강조하기 위해 돌기 섬유질형 나노실리카(Dendritic Fibrous Nanosilica, "DFNS") 라는 명칭을 사용함)의 표면에 효율적으로 Zn 기반 배위 고분자(Coordination Polymer) 층을 형성시킨 나노구조체 (DFNS@CP; 이하 본 발명의 설명 및 도면 등에서 "DFNS@ZIF-8" 또는 "DFNS@Zn_CPN" 으로 표현함)의 합성방법을 보고한다. 또한, 돌기 섬유질형 나노실리카 입자의 표면에 Au 층을 형성시킨 나노구조체(DFNS/Au 나노입자)의 표면에 배위 고분자 층을 형성시킨 나노구조체 (DFNS/Au@CP; 이하 본 발명의 설명 및 도면 등에서 "DFNS/Au@ZIF-8" 또는 "DFNS/Au@Zn_CPN"으로 표현함)의 합성 방법을 보고한다. 여러 가지 반응물과 실험 조건을 조절하여 배위 고분자 층의 구조를 조절할 수 있음을 보인다. 형성된 나노입자는 크노에베나겔 축합(Knoevenagel Condensation) 반응에 우수한 촉매반응효과를 보인다. In the present invention, the surface of silica nanoparticles having many branches and pores (in the present invention, the designation of dendritic fibrous nanosilica ("DFNS") is used to emphasize the fact that it exhibits a protruding large surface) Synthesis method of nanostructures (DFNS @ CP; hereinafter referred to as "DFNS @ ZIF-8" or "DFNS @ Zn_CPN" in the description and drawings of the present invention) to efficiently form a Zn-based coordination polymer layer report. In addition, a nanostructure (DFNS / Au @ CP; a coordination polymer layer is formed on the surface of a nanostructure (DFNS / Au nanoparticle) in which an Au layer is formed on the surface of a protruding fibrous nanosilica particle (DFNS / Au @ CP; hereinafter, description and drawings of the present invention) Et al. (DFNS / Au @ ZIF-8) or "DFNS / Au @ Zn_CPN"). It is shown that the structure of the coordination polymer layer can be controlled by controlling various reactants and experimental conditions. The formed nanoparticles show an excellent catalytic reaction effect on the Knoevenagel Condensation reaction.
본 발명에서는 돌기 섬유질형 나노실리카 주름이 형성된 실리카 나노입자(Dendritic Fibrous Nanosilica, 이하 "DFNS"와 혼용함)를 합성하고 이를 주형(template)으로 사용하여 DFNS 기반의 하이브리드 나노입자를 합성하였다.In the present invention, synthetic nanoparticles having dendritic fibrous nanosilica wrinkles (Dendritic Fibrous Nanosilica, hereinafter referred to as "DFNS") were synthesized and used as a template to synthesize DFNS-based hybrid nanoparticles.
본 발명은 The present invention
입경 200~600nm의 돌기 섬유질형 나노실리카 코어 및 Protruding fibrous nano-silica core with a particle size of 200 ~ 600nm and
상기 코어의 외주면에 형성되며, 두께는 30~1000nm이며, DMF 용액에서 2-메틸이미다졸 및 Zn2 +의 반응에 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 {2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가하여 형성한 Zn 기반 배위 고분자 (Zn-based coordination polymer) 쉘을 포함하는 나노입자에 관한 것이다. It is formed on the outer peripheral surface of the core, a thickness of 30 ~ 1000nm, and the reaction of the 2,6-bis 2-methylimidazole and Zn 2 + in a DMF solution [(4-carboxy-anilino) carbonyl] pyridin-2 { , 6-bis [(4-carboxyanilino) carbonyl] pyridine} It is related to nanoparticles including a Zn-based coordination polymer shell formed by adding a ligand.
상기 기재한 코어의 입경 및 쉘의 두께는 본 발명자들의 실험을 통해 얻은 측정값 범위이다.The particle diameter of the core and the thickness of the shell described above are a range of measured values obtained through experiments by the present inventors.
또한, 본 발명은 상기 돌기 섬유질형 나노실리카 코어와 Zn 기반 배위 고분자 쉘 사이에 공간이 존재함을 특징으로 하는 나노입자에 관한 것이다. In addition, the present invention relates to nanoparticles characterized in that a space exists between the protruding fibrous nanosilica core and the Zn-based coordinating polymer shell.
또한, 본 발명은 상기 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 리간드를 농도 0.01M 내지 0.05M로 가함을 특징으로 하는 나노입자에 관한 것이다. 위 [N3] 리간드 농도 범위에서는 높은 농도일수록 입자의 크기가 커졌다. In addition, the present invention relates to nanoparticles characterized in that the 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine ligand is added at a concentration of 0.01M to 0.05M. In the above [N3] ligand concentration range, the higher the concentration, the larger the particle size.
또한, 본 발명은 상기 Zn2 + : 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 : 2-메틸이미다졸의 몰비가 2:1:3 ~ 2:2:3임을 특징으로 하는 나노입자에 관한 것이다. 이 범위의 몰비에서 위 나노입자가 가장 잘 형성되었다.In addition, the present invention is characterized in that the molar ratio of Zn 2 + : 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine: 2-methylimidazole is 2: 1: 3 to 2: 2: 3. It relates to the nanoparticles. The above nanoparticles were best formed in this range of molar ratios.
또한, 본 발명은 입경 200~600nm의 돌기 섬유질형 나노실리카 코어 및In addition, the present invention is a protruding fibrous nanosilica core having a particle size of 200 to 600 nm
상기 코어의 외주면에 형성되며, 두께는 30~1000nm이며, 메탄올 용액에서 2-메틸이미다졸 및 Zn2 +의 반응으로 형성한 Zn 기반 배위 고분자 ZIF-8 쉘을 포함하는 나노입자에 관한 것이다. 상기 기재한 코어의 입경 및 쉘의 두께는 본 발명자들의 실험을 통해 얻은 측정값 범위이다.Is formed on the outer peripheral surface of the core, the thickness is 30 ~ 1000nm, relates to nanoparticles comprising a Zn-based coordination polymer shell, a ZIF-8 is formed by the reaction of 2-methyl imidazole, and Zn + 2 in methanol solution. The particle diameter of the core and the thickness of the shell described above are a range of measured values obtained through experiments by the present inventors.
또한, 본 발명은 상기 Zn2 + : 2-메틸이미다졸의 몰비가 1:2임을 특징으로 하는 나노입자에 관한 것이다. 몰비 1:2일 때 이 나노입자가 가장 잘 형성되었다.In addition, the present invention relates to nanoparticles characterized in that the molar ratio of Zn 2 + : 2-methylimidazole is 1: 2. When the molar ratio was 1: 2, these nanoparticles were best formed.
또한, 본 발명은 상기 돌기 섬유질형 나노실리카 코어와 Zn 기반 배위 고분자 ZIF-8 쉘 사이에 공간이 존재함을 특징으로 하는 나노입자에 관한 것이다.In addition, the present invention relates to nanoparticles characterized in that a space exists between the protruding fibrous nanosilica core and the Zn-based coordination polymer ZIF-8 shell.
또한, 본 발명은 입경 200~600nm의 돌기 섬유질형 나노실리카 표면에 1~5nm의 금 나노닷이 분포되어 있는 돌기 섬유질형 나노실리카/금 나노닷 코어, 상기 코어의 외주면에 형성되며, DMF 용액에서 2-메틸이미다졸, Zn2 + 및 2,6-비스[(4-카복시아닐리노)카보닐]피리딘{2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가하여 반응시켜 형성한, 두께 30~1000nm의 Zn 기반 배위 고분자 쉘을 포함하는 나노입자에 관한 것이다. 이 코어의 입경, 금 나노닷의 크기 및 쉘의 두께는 본 발명자들의 실험을 통해 얻은 측정값 범위이다. In addition, the present invention is formed on the outer circumferential surface of the protruding fibrous nano-silica / gold nano-dot core, in which 1 to 5 nm of gold nano-dots are distributed on the surface of the protruding fibrous nano-silica having a particle diameter of 200 to 600 nm. formed by the reaction of 2-methyl imidazole was added to, Zn + 2 and 2,6-bis [(4-carboxy-anilino) carbonyl] pyridine {2,6-bis [(4- carboxyanilino) carbonyl] pyridine} ligand One, it relates to a nanoparticle comprising a Zn-based coordination polymer shell having a thickness of 30 ~ 1000nm. The particle diameter of this core, the size of the gold nanodots and the thickness of the shell are a range of measurements obtained through our experiments.
또한, 본 발명은 입경 200~600nm의 돌기 섬유질형 나노실리카 표면에 5~30nm의 금 나노입자가 다수 분포되어 있는 돌기 섬유질형 나노실리카/금 나노입자 코어, 상기 코어의 외주면에 형성되며, DMF 용액에서 2-메틸이미다졸, Zn2 + 및 2,6-비스[(4-카복시아닐리노)카보닐]피리딘{2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가하여 반응시켜 형성한, 두께 30~1000nm의 Zn 기반 배위 고분자 쉘을 포함하는 나노입자에 관한 것이다. 이 코어의 입경, 금 나노입자의 크기 및 쉘의 두께는 본 발명자들의 실험을 통해 얻은 측정값 범위이다. In addition, the present invention is formed on the outer circumferential surface of the protruding fibrous nanosilica / gold nanoparticle core in which a large number of gold nanoparticles of 5-30 nm are distributed on the surface of the protruding fibrous nanosilica having a particle diameter of 200 to 600 nm, and the DMF solution. 2-methylimidazole was added by reacting the imidazole, Zn + 2 and 2,6-bis [(4-carboxy-anilino) carbonyl] pyridine {2,6-bis [(4- carboxyanilino) carbonyl] pyridine} ligand in It relates to nanoparticles comprising a Zn-based coordination polymer shell having a thickness of 30 to 1000 nm. The particle diameter of this core, the size of the gold nanoparticles, and the thickness of the shell are a range of measurements obtained through our experiments.
또한, 본 발명은 상기 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 리간드를 0.01M 내지 0.05M 가함을 특징으로 하는 나노입자에 관한 것이다.In addition, the present invention relates to nanoparticles characterized in that the 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine ligand is added at 0.01M to 0.05M.
또한, 본 발명은 상기 Zn2 + : 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 : 2-메틸이미다졸의 몰비가 2:1:3 ~ 2:2:3임을 특징으로 하는 나노입자에 관한 것이다.In addition, the present invention is characterized in that the molar ratio of Zn 2 + : 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine: 2-methylimidazole is 2: 1: 3 to 2: 2: 3. It relates to the nanoparticles.
또한, 본 발명은 상기 코어와 배위 고분자 쉘 사이에 공간이 존재함을 특징으로 하는 나노입자에 관한 것이다.In addition, the present invention relates to nanoparticles characterized in that a space exists between the core and the coordinating polymer shell.
또한, 본 발명은 입경 200~600nm의 돌기 섬유질형 나노실리카 표면에 5~30nm의 금 나노입자가 분포되어 있는 돌기 섬유질형 나노실리카/금 나노입자 코어, 상기 코어의 외주면에 형성되며, 메탄올 용액에서 2-메틸이미다졸 및 Zn2 +의 반응으로 형성한, 두께 30~1000nm의 Zn 기반 배위 고분자 쉘을 포함하는 나노입자에 관한 것이다. 이 코어의 입경, 금 나노입자의 크기 및 쉘의 두께는 본 발명자들의 실험을 통해 얻은 측정값 범위이다. In addition, the present invention is formed on the outer circumferential surface of the protruding fibrous nanosilica / gold nanoparticle core, in which gold nanoparticles of 5-30 nm are distributed on the surface of the protruding fibrous nanosilica having a particle size of 200-600 nm, in a methanol solution. one is formed by the reaction of 2-methyl imidazole, and Zn + 2, relates to nanoparticles comprising a Zn-based coordination polymer shell with a thickness of 30 ~ 1000nm. The particle diameter of this core, the size of the gold nanoparticles, and the thickness of the shell are a range of measurements obtained through our experiments.
또한, 본 발명은 상기 Zn2 + : 2-메틸이미다졸의 몰비가 1:2임을 특징으로 하는 나노입자에 관한 것이다.In addition, the present invention relates to nanoparticles characterized in that the molar ratio of Zn 2 + : 2-methylimidazole is 1: 2.
또한, 본 발명은 상기 코어와 쉘 사이에 공간이 형성됨을 특징으로 한다.In addition, the present invention is characterized in that a space is formed between the core and the shell.
또한, 본 발명은 상기 여러 종류의 나노입자 중 1종의 나노입자를 포함하는 촉매에 관한 것이다.In addition, the present invention relates to a catalyst comprising one type of nanoparticles among the various types of nanoparticles.
본 발명에 의한 DFNS@CP 나노입자 또는 DFNS/Au@CP 나노입자는 합성시 가하는 2-메틸이미다졸 및 Zn2 +의 농도에 따라 배위 고분자 레이어 두께를 조절할 수 있다.DFNS @ CP nanoparticles or DFNS / Au @ CP nanoparticles according to the present invention can control the coordination polymer layer thickness in accordance with 2-methylimidazole and the concentration of Zn + 2 applied in the synthesis.
본 발명에 의해 합성된 DFNS@CP 나노입자 또는 DFNS/Au@CP 나노입자는 나노실리카 코어와 배위 고분자 레이어 사이에 공간이 형성되어 있어 촉매 활성에 유용하다.The DFNS @ CP nanoparticles or DFNS / Au @ CP nanoparticles synthesized by the present invention are useful for catalytic activity because a space is formed between the nanosilica core and the coordinating polymer layer.
본 발명에 의해 합성된 DFNS/Au@CP 나노입자는 Au 나노입자가 실리카 코어 표면에 존재하며 배위 고분자에 의해 보호되고 있으므로 안정한 촉매제 형성에 유용하다. The DFNS / Au @ CP nanoparticles synthesized by the present invention are useful for forming a stable catalyst since Au nanoparticles are present on the surface of the silica core and are protected by a coordination polymer.
본 발명에 의해 합성된 DFNS@CP 나노입자 또는 DFNS/Au@CP 나노입자는 본 발명의 합성방법에 의해 크기를 조절할 수 있으므로 다양한 용도에 적합한 크기로 합성할 수 있다. The DFNS @ CP nanoparticles or DFNS / Au @ CP nanoparticles synthesized by the present invention can be sized by the synthesis method of the present invention, and thus can be synthesized in a size suitable for various uses.
본 발명에 의해 합성된 DFNS@Zn_CPN 나노입자 또는 DFNS/Au@Zn_CPN 나노입자는 [N3] 리간드에 다른 금속이온을 배위할 수 있으므로 기능과 성질이 다양한 재료물질을 합성할 수 있다.The DFNS @ Zn_CPN nanoparticles or DFNS / Au @ Zn_CPN nanoparticles synthesized by the present invention can coordinate other metal ions to the [N3] ligand, thereby synthesizing material materials having various functions and properties.
도 1은 DFNS@Zn_CPN 나노입자를 합성하는 화학반응식과 DFNS@Zn_CPN 나노입자의 주사전자현미경(SEM) 이미지((a), (b)) 및 투과전자현미경(TEM) 이미지((c), (d))이다. (d)의 각각의 그림은 EDS(energy-dispersive x-ray spectroscopy) 맵핑(mapping) 분석 결과(질소(N), 규소(Si), 탄소(C), 산소(O), 아연(Zn) 원소 측정 이미지)이다. 스케일바: (a) 500nm, (b-d) 250nm.
도 2 (a)는 DFNS@Zn_CPN 나노입자와 Zn_CPN, DFNS의 분말 X선 회절(Powder X-ray diffraction; PXRD), (b)는 비표면적 분석장비(Brunauer Emmett Teller, BET)로 분석한 질소 흡착 그래프(온도 77K), (c)는 적외선(IR) 분광 스펙트라, (d)는 자외선-가시광선(UV-vis) 흡광도 스펙트라이다.
도 3은 반응 사이클을 반복하여 크기를 조절하며 합성된 DFNS@Zn_CPN 나노입자의 SEM 이미지와 크기분포 히스토그램이다. 평균 직경은 1 cycle: 589±66nm (178개의 입자를 측정한 값), 2 cycle: 646±49nm (169개의 입자를 측정한 값), 3 cycle: 667±44nm (97개의 입자를 측정한 값), 4 cycle: 719±76nm (152개의 입자를 측정한 값), 5 cycle: 819±42nm (130개의 입자를 측정한 값).
도 4 (a), (b)는 DFNS@ZIF-8 나노입자의 SEM 이미지이다. (c)는 DFNS와DFNS@ZIF-8 나노입자의 분말 X선 회절 (PXRD) 분석 결과와 시뮬레이션된 ZIF-8 그래프이다.
도 5는 DFNS/Au dot@Zn_CPN 나노입자를 합성하는 화학반응식과 DFNS/Au dot@Zn_CPN 나노입자의 SEM 이미지 (a)와 DFNS/Au dot@Zn_CPN 나노입자의 직경을 측정한 히스토그램 (b)이다. (c)는 나노입자의 투과전자현미경(TEM) 명시야 (bright field) 이미지이다. (d)는 EDS 맵핑(mapping) 분석 결과 (금(Au), 실리콘 (Si), 아연 (Zn), 탄소 (C), 질소 (N) 원소의 측정의 이미지)이다.
도 6은 DFNS/Au dot@Zn_CPN과 DFNS/Au dot 입자의 분말 X선 회절분석 (PXRD) 결과 (a)와 비표면적 분석장비(Brunauer Emmett Teller, BET)로 분석한 DFNS/Au dot@Zn_CPN의 질소 흡착 그래프 (온도 77K) (b), DFNS/Au dot@Zn_CPN과 DFNS/Au dot 입자의 적외선 (IR) 분광 스펙트라 (c), 자외선-가시광선 (UV-vis) 흡광도 스펙트라이다.
도 7은 DFNS/Au@Zn_CPN 나노입자를 합성하는 화학반응식과 (a) DFNS/Au@Zn_CPN 나노입자의 SEM 이미지, (b) 나노입자 직경을 측정한 히스토그램, (c) 나노입자의 투과전자현미경(TEM) 이미지, (d) EDS 맵핑 (mapping) 분석결과 (금(Au), 규소(Si), 산소(O), 아연(Zn), 탄소(C), 질소(N) 원소 측정 이미지이다.
도 8 (a) DFNS/Au@Zn_CPN의 분말 X-선 회절 패턴이며, 상기 표시된 기호(*)는 금 금속의 회절 패턴에서 나타나는 피크이다 (JCPDS card no. 01-089-3697). (b) 77K에서 측정된 DFNS/Au@Zn_CPN의 질소 흡착 스펙트럼과 기공 크기 분포이다.
도 9는 DFNS/Au@ZIF-8의 SEM 이미지이다.
도 10은 톨루엔에 용해된 벤즈알데하이드의 검정곡선이다.
도 11은 DFNS/Au(녹색)의 크노에베나겔(Knoevenagel) 축합 반응에 대한 촉매 활성 결과이다. (DFNS/Au(녹색), DFNS/Au@ZIF-8(적색), DFNS/Au@Zn_CPN(청색)).1 is a chemical reaction scheme for synthesizing DFNS @ Zn_CPN nanoparticles, and scanning electron microscope (SEM) images ((a), (b)) and transmission electron microscope (TEM) images ((c), () of DFNS @ Zn_CPN nanoparticles. d)). Each picture in (d) is energy-dispersive x-ray spectroscopy (EDS). Mapping analysis results (nitrogen (N), silicon (Si), carbon (C), oxygen (O), zinc (Zn) elemental measurement image). Scale bar: (a) 500 nm, (bd) 250 nm.
Figure 2 (a) is a powder X-ray diffraction (PXRD) of DFNS @ Zn_CPN nanoparticles and Zn_CPN, DFNS, (b) nitrogen adsorption analyzed by a specific surface area analyzer (Brunauer Emmett Teller, BET) Graphs (temperature 77K), (c) are infrared (IR) spectral spectra, and (d) are ultraviolet-visible (UV-vis) absorbance spectra.
3 is a SEM image and size distribution histogram of synthesized DFNS @ Zn_CPN nanoparticles by adjusting the size by repeating the reaction cycle. The average diameter is 1 cycle: 589 ± 66nm (measurement of 178 particles), 2 cycle: 646 ± 49nm (measurement of 169 particles), 3 cycle: 667 ± 44nm (measurement of 97 particles) , 4 cycles: 719 ± 76nm (measured 152 particles), 5 cycles: 819 ± 42nm (measured 130 particles).
4 (a) and (b) are SEM images of DFNS @ ZIF-8 nanoparticles. (c) is a powder X-ray diffraction (PXRD) analysis result of DFNS and DFNS @ ZIF-8 nanoparticles and a simulated ZIF-8 graph.
5 is a chemical reaction scheme for synthesizing DFNS / Au dot @ Zn_CPN nanoparticles and a SEM image (a) of DFNS / Au dot @ Zn_CPN nanoparticles and a histogram (b) measuring diameters of DFNS / Au dot @ Zn_CPN nanoparticles. . (c) is a transmission electron microscope (TEM) bright field image of nanoparticles. (d) is an EDS mapping analysis result (image of measurement of elements of gold (Au), silicon (Si), zinc (Zn), carbon (C), nitrogen (N)).
Figure 6 shows the results of powder X-ray diffraction analysis (PXRD) of DFNS / Au dot @ Zn_CPN and DFNS / Au dot particles (a) and DFNS / Au dot @ Zn_CPN analyzed by specific surface area analysis equipment (Brunauer Emmett Teller, BET). Nitrogen adsorption graph (temperature 77K) (b), infrared (IR) spectral spectra (c) of DFNS / Au dot @ Zn_CPN and DFNS / Au dot particles, and ultraviolet-visible (UV-vis) absorbance spectra.
7 is a chemical reaction formula for synthesizing DFNS / Au @ Zn_CPN nanoparticles, (a) SEM image of DFNS / Au @ Zn_CPN nanoparticles, (b) Histogram of nanoparticle diameter measurements, (c) Transmission electron microscope of nanoparticles (TEM) image, (d) EDS mapping analysis results (Measurement image of gold (Au), silicon (Si), oxygen (O), zinc (Zn), carbon (C), nitrogen (N)).
Fig. 8 (a) is a powder X-ray diffraction pattern of DFNS / Au @ Zn_CPN, and the symbol (*) indicated above is a peak appearing in the diffraction pattern of gold metal (JCPDS card no. 01-089-3697). (b) Nitrogen adsorption spectrum and pore size distribution of DFNS / Au @ Zn_CPN measured at 77K.
9 is an SEM image of DFNS / Au @ ZIF-8.
10 is a calibration curve of benzaldehyde dissolved in toluene.
FIG. 11 shows the catalytic activity results for Knoevenagel condensation reaction of DFNS / Au (green). (DFNS / Au (green), DFNS / Au @ ZIF-8 (red), DFNS / Au @ Zn_CPN (blue)).
아래에서는 구체적인 실시예를 들어 본 발명의 구성을 좀 더 자세히 설명한다. 그러나, 본 발명의 범위가 실시예의 기재에만 한정되는 것이 아님은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 자명하다.Hereinafter, the configuration of the present invention will be described in more detail with reference to specific examples. However, it is apparent to those skilled in the art that the scope of the present invention is not limited only to the description of the examples.
시약reagent
아세트산아연 (II) 이수화물 {Zinc (II) acetate dihydrate, Zn(OAc)2.2H2O, ≥ 98%, Sigma-Aldrich }, 2-메틸이미다졸(C4H6N2, ≥ 99%, Sigma-Aldrich), 세틸트리메틸암모늄 브로마이드{Cetyltrimethylammonium bromide, CH3(CH2)15N(CH3)3Br, 이하 "CTAB"와 혼용함, 99+%, Acros Organics}, 폴리옥시에틸렌글라이콜 도데실 에테르{Polyoxyethylene glycol dodecyl ether, (C2H4O)23C12H25OH, 이하 "Brij35"와 혼용함, Acros Organics}, 염화금산(Hydrogen tetrachloroauratetrihydrate, HAuCl4 ·3H2O, 99.9%, Sigma-Aldrich), 질산은(silver nitrate, AgNO3, 99+%, Sigma-Aldrich), 수소화붕소나트륨(sodium borohydride, NaBH4, 99.995%, Sigma-Aldrich), 아스코르브산(L-ascorbic acid, 99%, Sigma-Aldrich), APTES{3-(aminopropyl)triethoxysilane, 98%, Sigma-Aldrich}, 폴리비닐피롤리돈{polyvinylpyrolidone, (C6H9NO)n, PVP10, 평균분자량 10,000, Sigma-Aldrich}, 수산화암모늄(Ammonium hydroxide, NH4OH, 28-30wt%, Sigma-Aldrich), 테트라에틸오쏘실리케이트{tetraethylorthosilicate, (Si(OC2H5)4, TEOS, 98%, Sigma-Aldrich}, 벤즈알데하이드(benzaldehyde, C6H5CHO, 99%, Sigma-Aldrich)와 말로노니트릴 (malononitrile, CH2(CN)2), 99%, Sigma-Aldrich), N,N-다이메틸포름아마이드 (N,N-dimethylformamide; DMF, 99.99%, Burdick & Jackson), 아세토나이트릴(acetonitrile, CH3CN, 99.5%, Junsei), 톨루엔(Toluene, C6H5CH3, 99.99%, Burdick & Jackson), 사이클로헥산(cyclohexane, C6H12, 99%, Sigma-Aldrich), 요소{Urea, CO(NH2)2, 98%, Sigma-Aldrich}, 에탄올(EtOH, 99.99%, Burdick & Jackson), 메탄올(MeOH, 99.99%, Burdick & Jackson), 다이메틸설폭사이드(dimethyl sulfoxide, DMSO, 99.99%, Burdick & Jackson), 펜타놀{1-Penthanol, CH3(CH2)3CH2OH, 98%, Alfa Aesar}, 염산(HCl), 질산(HNO3), 아세톤(99.99%, Burdick & Jackson) 및 정제수는 구입한 그대로 사용하였다. 사용한 모든 화학제품은 더 정제하지 않고 사용하였다. 모든 반응 용액은 반응 전에 바로 준비하였다. 모든 유리 기구들은 사용하기 전에 왕수(염산과 질산의 3:1 부피비)로 씻고 3차 증류수로 충분히 헹구었다. Zinc (II) acetate dihydrate {Zinc (II) acetate dihydrate, Zn (OAc) 2 .2H 2 O, ≥ 98%, Sigma-Aldrich}, 2-methylimidazole (C 4 H 6 N 2 , ≥ 99 %, Sigma-Aldrich), Cetyltrimethylammonium bromide, CH 3 (CH 2 ) 15 N (CH 3 ) 3 Br, hereinafter mixed with "CTAB", 99 +%, Acros Organics}, polyoxyethylene Polyoxyethylene glycol dodecyl ether, (C 2 H 4 O) 23 C 12 H 25 OH, hereinafter mixed with "Brij35", Acros Organics}, Hydrogen tetrachloroauratetrihydrate, HAuCl 4 · 3H 2 O, 99.9%, Sigma-Aldrich, silver nitrate, AgNO 3 , 99 +%, Sigma-Aldrich, sodium borohydride, NaBH 4 , 99.995%, Sigma-Aldrich, L-ascorbic acid , 99%, Sigma-Aldrich), APTES {3- (aminopropyl) triethoxysilane, 98%, Sigma-Aldrich}, polyvinylpyrolidone, (C 6 H 9 NO) n , PVP10, average molecular weight 10,000, Sigma -Aldrich}, Ammonium hydroxide (NH 4 OH, 28-30wt%, Sigma-Aldrich), tetraethylorthosilicate, (Si (OC 2 H 5 ) 4 , TEOS, 98%, Sigma-Aldrich}, benzaldehyde, C 6 H 5 CHO, 99% , Sigma-Aldrich) and malononitrile (CH 2 (CN) 2 ), 99%, Sigma-Aldrich), N, N-dimethylformamide (N, N-dimethylformamide; DMF, 99.99%, Burdick & Jackson), acetonitrile (CH 3 CN, 99.5%, Junsei), toluene (C 6 H 5 CH 3 , 99.99%, Burdick & Jackson), cyclohexane (cyclohexane, C 6 H 12 , 99%, Sigma-Aldrich), Urea {Urea, CO (NH 2 ) 2 , 98%, Sigma-Aldrich}, Ethanol (EtOH, 99.99%, Burdick & Jackson), Methanol (MeOH, 99.99% , Burdick & Jackson), dimethyl sulfoxide (DMSO, 99.99%, Burdick & Jackson), fentanol {1-Penthanol, CH 3 (CH 2 ) 3 CH 2 OH, 98%, Alfa Aesar}, hydrochloric acid (HCl), nitric acid (HNO 3 ), acetone (99.99%, Burdick & Jackson) and purified water were used as purchased. All chemicals used were used without further purification. All reaction solutions were prepared immediately before the reaction. All glassware were washed with aq. (3: 1 volume ratio of hydrochloric acid and nitric acid) and rinsed thoroughly with tertiary distilled water before use.
약자: 2,6-bis[(4-carboxyanilino)carbonyl]pyridine = [N3], OAc = acetate, 2-Methylimidazole = 2-MeIM.Abbreviations: 2,6-bis [(4-carboxyanilino) carbonyl] pyridine = [N3], OAc = acetate, 2-Methylimidazole = 2-MeIM.
실시예 1: 돌기 섬유질형 나노실리카 (DFNS) 합성Example 1: Synthesis of projection fibrous nanosilica (DFNS)
돌기 섬유질형 나노실리카{Dendritic Fibrous Nanosilica, "DFNS"}의 합성은 종래 보고된 비슷한 형태의 나노구조체 논문의 실험법을 참고하여 진행하였다(1). 전형적인 합성법은 다음과 같다. 30㎖의 사이클로헥산(cyclohexane)과 1.5㎖의 펜타놀(1-penthanol)을 100㎖의 삼각 플라스크에 넣어 혼합하고, 이후 2.66㎖의 TEOS(tetraethylorthosilicate, 2.5g, 0.012mol)를 첨가하여 용해했다. 100㎖의 삼각 플라스크에 1g의 CTAB(cetyltrimethylammonium bromide, 0.0027mol)와 0.6g의 요소(0.01mol)를 넣은 후 30㎖의 3차 증류수를 첨가하여 모두 용해했다. 두 개의 삼각 플라스크에 담긴 혼합물을 한 곳으로 모은 다음, 실온(20℃)에서 2시간 동안 교반하였다. 그 후 혼합 용액을 테플론(teflon) 소재의 용기에 옮겨 담고 고온 및 고압 반응기인 오토클레이브(autoclaves)에 넣어 최대한 밀봉했다. 반응기를 온도 조절 오븐(temperature controls oven)에 넣고 120℃에서 6시간 동안 반응시켰다. 반응 완료 후 혼합액을 실온(20℃)까지 서서히 냉각하고, 5분간 3500rpm으로 원심분리하였다. 제조된 DFNS는 아세톤과 3차 증류수로 반복 세척하고 원심분리(5분간 13500rpm)하여 정제하였다. 정제 이후에는 실온에서 24시간 동안 건조하였고 건조가 끝난 DFNS는 550℃ 조건에서 6시간 동안 하소(calcination)하여 유기물과 계면활성제를 제거하였다.Synthesis of dendritic fibrous nanosilica ("DFNS") was performed by referring to the experimental method of a similarly reported nanostructured paper (1). A typical synthesis method is as follows. 30 ml of cyclohexane and 1.5 ml of pentanol were mixed in a 100 ml Erlenmeyer flask and then dissolved by adding 2.66 ml of tetraethylorthosilicate (2.5 g, 0.012 mol). After adding 1 g of CTAB (cetyltrimethylammonium bromide, 0.0027 mol) and 0.6 g of urea (0.01 mol) to a 100 mL Erlenmeyer flask, 30 mL of tertiary distilled water was added to dissolve them. The mixture contained in the two Erlenmeyer flasks was collected in one place, and then stirred at room temperature (20 ° C) for 2 hours. Thereafter, the mixed solution was transferred to a container made of Teflon and placed in an autoclaves, a high-temperature and high-pressure reactor, to be sealed as much as possible. The reactor was placed in a temperature control oven and reacted at 120 ° C. for 6 hours. After completion of the reaction, the mixed solution was gradually cooled to room temperature (20 ° C), and centrifuged at 3500 rpm for 5 minutes. The prepared DFNS was washed repeatedly with acetone and tertiary distilled water and purified by centrifugation (13500 rpm for 5 minutes). After purification, the mixture was dried at room temperature for 24 hours, and the dried DFNS was calcined at 550 ° C. for 6 hours to remove organic substances and surfactants.
실시예Example 2: 2: DFNSDFNS 나노입자의 Nanoparticle 아민Amine 기능화 Functionalization
합성된 DFNS 입자 30mg을 e-튜브에 옮긴 후 1㎖의 3차 증류수를 넣어 잘 분산하였다. 0.03㎖의 APTES와 0.1㎖의 NH4OH를 순서대로 첨가하고 실온(20℃)에서 12시간 동안 교반하였다. 반응이 완료된 후, 5분간 13500rpm으로 원심분리하였다. 제조된 입자는 3차 증류수로 반복 세척하고 원심분리(5분간 13500rpm)하여 정제한 이후 1㎖의 3차 증류수에 재분산하여 아민 기능화된 DFNS를 얻었다.After transferring 30 mg of the synthesized DFNS particles to the e-tube, 1 ml of tertiary distilled water was added to disperse them well. 0.03 ml of APTES and 0.1 ml of NH 4 OH were added sequentially and stirred at room temperature (20 ° C.) for 12 hours. After the reaction was completed, it was centrifuged at 13500 rpm for 5 minutes. The prepared particles were repeatedly washed with tertiary distilled water, purified by centrifugation (13500 rpm for 5 minutes), and redispersed in 1 mL of tertiary distilled water to obtain amine functionalized DFNS.
실시예Example 3: 돌기 3: Turning 섬유질형Fiber type 나노실리카Nano silica /금 /gold 나노닷Nano Dot 혼성 나노입자 ( Hybrid nanoparticles ( DFNSDFNS /Au / Au 나노닷Nano Dot ) 합성) synthesis
1㎖의 아민 기능화된 DFNS 수용액에 0.3㎖의 HAuCl4(0.025M, 7.5μmol)를 첨가하고 실온(20℃)에서 30분 동안 교반하였다. 이후 원심분리(5분간 13500rpm)하여 상층액을 제거하고 1㎖의 3차 증류수에 재분산하였다. 얼음 용기에 담긴 NaBH4(aq)(0.1M, 0.05mmol) 0.5㎖를 천천히 첨가하고 실온(20℃)에서 12시간 동안 교반하였다. 반응이 완료된 후 10분간 3500rpm으로 원심분리하였고, 분리한 입자는 3차 증류수로 반복 세척하고 원심분리(5분간 13500rpm)하여 정제하였다.0.3 ml of HAuCl 4 (0.025M, 7.5 μmol) was added to 1 ml of an amine functionalized DFNS aqueous solution and stirred at room temperature (20 ° C.) for 30 minutes. Then, the supernatant was removed by centrifugation (13500 rpm for 5 minutes) and redispersed in 1 ml of tertiary distilled water. 0.5 ml of NaBH 4 (aq) (0.1M, 0.05 mmol) in an ice container was slowly added and stirred at room temperature (20 ° C.) for 12 hours. After the reaction was completed, it was centrifuged at 3500 rpm for 10 minutes, and the separated particles were repeatedly washed with tertiary distilled water and purified by centrifugation (13500 rpm for 5 minutes).
실시예Example 4: 돌기 4: turning 섬유질형Fiber type 나노실리카Nano silica /금 혼성 (/ Gold hybrid ( DFNSDFNS /Au) 나노입자 합성/ Au) Nanoparticle synthesis
DFNS/Au 나노입자의 합성에서 시드 매개법(seed mediated growth method)을 사용하여 실리카 표면에 붙은 금 입자의 크기와 전체 입자의 형태를 조절하였다. 시드 매개법을 이용한 DFNS/Au 나노입자의 합성에서 금 시드(Au seed)로 DFNS/Au 닷(dot) 입자를 사용하였다. DFNS/Au 닷 입자 합성을 위해 1㎖의 DFNS/NH2 수용액에 0.3㎖의 HAuCl4(0.025M, 7.5μmol)를 첨가하고 실온(20℃)에서 30분 동안 교반하였다. 이후 원심분리(5분간 13500rpm)하여 상층액을 제거하고 1㎖의 3차 증류수에 재분산하였다. 0.5㎖의 얼음 용기에 담긴 NaBH4(aq)(0.1M, 0.05mmol)를 천천히 첨가하고 실온(20℃)에서 12시간 동안 교반하였다. 반응이 완료된 후 10분간 3500rpm으로 원심분리하였고, 분리한 입자는 3차 증류수로 반복 세척하고 원심분리(5분간 13500rpm)하여 정제하여 DFNS/Au 닷 입자를 얻었다.In the synthesis of DFNS / Au nanoparticles, a seed mediated growth method was used to control the size of the gold particles attached to the silica surface and the shape of the whole particles. In the synthesis of DFNS / Au nanoparticles using a seed mediating method, DFNS / Au dot particles were used as Au seeds. For synthesis of DFNS / Au dot particles, 0.3 ml of HAuCl 4 (0.025M, 7.5 μmol) was added to 1 ml of DFNS / NH 2 aqueous solution and stirred at room temperature (20 ° C.) for 30 minutes. Then, the supernatant was removed by centrifugation (13500 rpm for 5 minutes) and redispersed in 1 ml of tertiary distilled water. NaBH 4 (aq) (0.1M, 0.05 mmol) in a 0.5 mL ice container was slowly added and stirred at room temperature (20 ° C.) for 12 hours. After the reaction was completed, centrifugation was performed at 3500 rpm for 10 minutes, and the separated particles were repeatedly washed with tertiary distilled water and purified by centrifugation (13500 rpm for 5 minutes) to obtain DFNS / Au dot particles.
시드 매개법을 이용한 DFNS/Au 나노입자의 합성법은 2종 이상의 성장 용액이 필요하다. 이 실험에서는 2개의 성장용액을 통하여 합성을 진행하였다. 첫 번째 성장용액 (A)로 1㎖의 Brij35(200mM) 수용액과 1㎖의 CTAB(100mM) 수용액을 혼합한 이중 계면활성제 수용액을 준비하고 0.2㎖의 3차 증류수를 첨가한 후 초음파 분쇄기를 사용하여 5분간 혼합하였다. 이후에 10㎕의 AgNO3(10mM) 수용액, 80㎕의 HAuCl4(10mM) 수용액, 30㎕의 아스코르브산(100mM) 수용액을 순차적으로 넣어 용액을 준비하였다. 두 번째 성장용액 (B)는 성장용액 (A)와 동일한 성분으로 구성되지만 부피만 10배로 하여 준비하였다{10㎖의 Brij35(200mM) 수용액, 10㎖의 CTAB(100mM) 수용액, 2㎖의 3차 증류수, 100㎕의 AgNO3(10mM) 수용액, 800㎕의 HAuCl4(10mM) 수용액, 300㎕의 아스코르브산(100mM) 수용액}. 성장용액 (A)에 시드 역할을 하는 DFNS/Au 닷 용액 200㎕를 첨가해주고 빠르게 흔들어 잘 혼합되게 하였다. 이후 성장용액 (A)의 색깔이 변하기 전 200㎕를 취하여 성장용액 (B)에 첨가하고 3~4회 잘 흔들어 용액이 잘 혼합되게 하였다. 이후 입자의 합성을 완료하기 위해 실온(20℃)에서 14시간 동안 보관하였다. 반응이 완료된 이후 입자의 특성 분석 및 다음 단계의 실험을 위해 2㎖를 취하여 e-튜브에 담아 원심분리(10min, 6000rpm) 하였고, 이후 3차 증류수로 2회 세척하였다.The method of synthesizing DFNS / Au nanoparticles using a seed mediating method requires two or more growth solutions. In this experiment, synthesis was performed through two growth solutions. As the first growth solution (A), a double surfactant aqueous solution in which 1 ml of Brij35 (200 mM) and 1 ml of CTAB (100 mM) was mixed was prepared, 0.2 ml of tertiary distilled water was added, and then an ultrasonic grinder was used. Mix for 5 minutes. Thereafter, 10 μl of AgNO 3 (10 mM) aqueous solution, 80 μl of HAuCl 4 (10 mM) aqueous solution, and 30 μl of ascorbic acid (100 mM) aqueous solution were sequentially added to prepare a solution. The second growth solution (B) was composed of the same components as the growth solution (A), but was prepared by doubling the volume (10 mL Brij35 (200 mM) aqueous solution, 10 mL CTAB (100 mM) aqueous solution, 2 mL tertiary Distilled water, 100 μl AgNO 3 (10 mM) aqueous solution, 800 μl HAuCl 4 (10 mM) aqueous solution, 300 μl ascorbic acid (100 mM aqueous solution)}. To the growth solution (A), 200 μl of a DFNS / Au dot solution serving as a seed was added and shaken quickly to mix well. Then, before changing the color of the growth solution (A), 200 μl was taken and added to the growth solution (B) and shaken well 3-4 times to mix well. Then, the particles were stored at room temperature (20 ° C.) for 14 hours to complete the synthesis of the particles. After the reaction was completed, 2 ml was taken for characterization of particles and the experiment of the next step, and centrifuged (10 min, 6000 rpm) in an e-tube, and then washed twice with tertiary distilled water.
합성 단계에서 다양한 농도의 HAuCl4(aq)를 첨가하여 실리카 표면에 성장하는 금 나노 입자를 제어하였다. 또한, 시드로 사용되었던 DFNS/Au 닷 입자에 포함된 Au 이온의 몰수와 성장용액(B를 기준)에 첨가되는 Au 이온의 몰수를 몰수비로 나누어 비율을 계산하였다.In the synthesis step, various concentrations of HAuCl 4 (aq) were added to control gold nanoparticles growing on the silica surface. In addition, the ratio was calculated by dividing the number of moles of Au ions contained in the DFNS / Au dot particles used as seeds and the number of moles of Au ions added to the growth solution (based on B) by the molar ratio.
실시예Example 5: DFNS@Zn_CPN 나노입자 합성 5: DFNS @ Zn_CPN nanoparticle synthesis
아민 기능화된 DFNS 입자의 DMF 현탁액(0.15mL)을 500rpm에서 15분 동안 교반하면서 아연 아세테이트(0.50mL, 0.050M)의 DMF 용액과 혼합하였다. 상기 혼합물에, [N3] 리간드(0.25mL, 0.050M) 및 2-MeIM(0.75mL, 0.050M)의 DMF 용액을 연속적으로 도입하였다. Zn2 +:[N3]:2-MeIM의 몰비는 2:1:3이다. 반응 혼합물을 500rpm에서 15분 동안 연속적으로 교반하였다. 그 후 80℃로 8시간 동안 유지했다. 반응 완료 후, 얻은 생성물을 원심분리에 의해 수집하고, DMF, 아세톤으로 수 회 세척한 다음, 진공에서 24시간 동안 건조하였다.A DMF suspension of amine functionalized DFNS particles (0.15 mL) was mixed with a DMF solution of zinc acetate (0.50 mL, 0.050 M) with stirring at 500 rpm for 15 minutes. To the mixture, a DMF solution of [N3] ligand (0.25 mL, 0.050M) and 2-MeIM (0.75mL, 0.050M) was continuously introduced. The molar ratio of Zn 2 + : [N3]: 2-MeIM is 2: 1: 3. The reaction mixture was stirred continuously at 500 rpm for 15 minutes. Then, it was kept at 80 ° C for 8 hours. After completion of the reaction, the obtained product was collected by centrifugation, washed several times with DMF and acetone, and then dried in vacuum for 24 hours.
DFNS@Zn_CPN의 배위 고분자층 두께는 반복적인 합성의 횟수에 의해 구현된다. 각 사이클에서 DFNS@Zn_CPN의 DMF 현탁액은 최신 DFNS@Zn_CPN을 DMF 0.15mL에 분산시킴으로써 얻어지지만, 다른 실험 조건은 변함없이 유지된다.The coordination polymer layer thickness of DFNS @ Zn_CPN is realized by the number of iterative synthesis. The DMF suspension of DFNS @ Zn_CPN in each cycle was obtained by dispersing the latest DFNS @ Zn_CPN in 0.15 mL of DMF, but other experimental conditions remained unchanged.
실시예Example 6: DFNS@ZIF-8 나노입자 합성 6: DFNS @ ZIF-8 nanoparticle synthesis
아민 기능화된 DFNS 입자의 메탄올 현탁액(0.15mL)을 500rpm에서 15분 동안 교반하면서 질산 아연(0.50mL, 0.050M)의 메탄올 용액과 혼합하였다. 반응 혼합물을 실온에서 24시간 동안 유지하였다. 그 후, 메탄올 중 2-MeIM(1.00mL, 0.050M)을 Zn2+:2-MeIM = 1:2의 몰비에 상응하게 투입했다. 반응 혼합물을 닫힌 상태에서 500rpm에서 15분 동안 연속적으로 교반하였다. 반응 완료 후, 얻어진 생성물을 원심분리로 수집하고 메탄올, 아세톤으로 수 회 세척한 다음 24시간 동안 진공 건조하였다.A methanol suspension (0.15 mL) of amine functionalized DFNS particles was mixed with a methanol solution of zinc nitrate (0.50 mL, 0.050 M) with stirring at 500 rpm for 15 minutes. The reaction mixture was kept at room temperature for 24 hours. Then, 2-MeIM (1.00 mL, 0.050M) in methanol was added correspondingly to a molar ratio of Zn 2+ : 2-MeIM = 1: 2. The reaction mixture was stirred continuously at 500 rpm for 15 minutes in a closed state. After completion of the reaction, the obtained product was collected by centrifugation, washed several times with methanol and acetone, and then vacuum dried for 24 hours.
실시예Example 7: 7: DFNSDFNS /Au dot@Zn_CPN 나노입자 합성/ Au dot @ Zn_CPN Nanoparticle synthesis
DFNS/Au dot@Zn_CPN 나노입자는 DFNS/Au dot 입자와 DMF 용매 중 Zn2 +, 2-MeIM 및 [N3] 리간드의 반응에 의해 합성된다. DFNS/Au dot 입자는 우선적으로 아민 기능화하였다. 합성된 DFNS/Au dot 입자 30mg을 e-튜브에 옮긴 후 1㎖의 3차 증류수를 넣어 잘 분산하였다. 0.03㎖의 APTES와 0.1㎖의 NH4OH를 순서대로 첨가하고 실온(20℃)에서 12시간 동안 교반하였다. 반응이 완료된 후, 5분간 13500rpm으로 원심분리하였다. 제조된 입자는 3차 증류수로 반복 세척하고 원심분리(5분간 13500rpm)하여 정제한 이후 1㎖의 3차 증류수에 재분산하여 아민 기능화된 DFNS/Au dot 입자를 얻었다. DFNS / Au dot @ Zn_CPN nanoparticles are synthesized by the reaction of Zn 2 +, 2-MeIM and [N3] ligand of DFNS / Au dot particles and a solvent DMF. DFNS / Au dot particles were preferentially amine functionalized. After transferring 30 mg of the synthesized DFNS / Au dot particles to the e-tube, 1 ml of tertiary distilled water was added to disperse them well. 0.03 ml of APTES and 0.1 ml of NH 4 OH were added sequentially and stirred at room temperature (20 ° C.) for 12 hours. After the reaction was completed, it was centrifuged at 13500 rpm for 5 minutes. The prepared particles were repeatedly washed with tertiary distilled water, purified by centrifugation (13500 rpm for 5 minutes), and then redispersed in 1 mL of tertiary distilled water to obtain amine-functionalized DFNS / Au dot particles.
4mL 바이얼에서 아민 기능화된 DFNS/Au dot 나노입자의 DMF 현탁액(0.15mL)을 500rpm에서 15분 동안 교반하면서 아세트산 아연(0.50mL, 0.050M)의 DMF 용액과 혼합했다. 상기 혼합물에, [N3] 리간드(0.25mL, 0.050M) 및 2-MeIM(0.75mL, 0.050M)의 DMF 용액을 연속적으로 도입하였다. Zn2 +:[N3]:2-MeIM의 몰비는 2:1:3이다. 반응 혼합물을 500rpm에서 15분 동안 연속적으로 교반하였다. 그 후 80℃의 온도에서 8시간 동안 유지했다. 반응 완료 후, 얻은 생성물을 원심분리로 수집하고, DMF, 아세톤으로 수 회 세척한 다음, 진공하에 24시간 동안 건조하였다.A DMF suspension of amine functionalized DFNS / Au dot nanoparticles (0.15 mL) in a 4 mL vial was mixed with a DMF solution of zinc acetate (0.50 mL, 0.050 M) with stirring at 500 rpm for 15 minutes. To the mixture, a DMF solution of [N3] ligand (0.25 mL, 0.050M) and 2-MeIM (0.75mL, 0.050M) was continuously introduced. The molar ratio of Zn 2 + : [N3]: 2-MeIM is 2: 1: 3. The reaction mixture was stirred continuously at 500 rpm for 15 minutes. After that, it was kept at a temperature of 80 ° C. for 8 hours. After completion of the reaction, the obtained product was collected by centrifugation, washed several times with DMF and acetone, and then dried under vacuum for 24 hours.
실시예Example 8: 8: DFNSDFNS /Au@Zn_CPN 나노입자 합성/ Au @ Zn_CPN nanoparticle synthesis
DFNS/Au@Zn_CPN 나노입자는 실시예 4에서 합성된 DFNS/Au 나노입자와 DMF 용매 중 Zn2 +, 2-MeIM 및 [N3] 리간드의 반응에 의해 합성된다. DFNS/Au dot 입자는 우선적으로 아민 기능화했다. 합성된 DFNS/Au 입자 30mg을 e-튜브에 옮긴 후 1㎖의 3차 증류수를 넣어 잘 분산하였다. 0.03㎖의 APTES와 0.1㎖의 NH4OH를 순차적으로 첨가하고 실온(20℃)에서 12시간 동안 교반하였다. 반응이 완료된 후, 5분간 13500rpm으로 원심분리하였다. 제조된 입자는 3차 증류수로 반복 세척하고 원심분리(5분간 13500rpm)하여 정제한 이후 1㎖의 3차 증류수에 재분산하여 아민 기능화된 DFNS/Au dot 입자를 얻었다.DFNS / Au @ Zn_CPN nanoparticles are synthesized by the reaction of the DFNS / Au nanoparticles and DMF Zn 2 +, 2-MeIM and [N3] ligand in the solvent prepared in Example 4. DFNS / Au dot particles were primarily amine functionalized. After transferring 30 mg of the synthesized DFNS / Au particles to an e-tube, 1 ml of tertiary distilled water was added thereto and dispersed well. 0.03 ml of APTES and 0.1 ml of NH 4 OH were sequentially added and stirred at room temperature (20 ° C.) for 12 hours. After the reaction was completed, it was centrifuged at 13500 rpm for 5 minutes. The prepared particles were repeatedly washed with tertiary distilled water, purified by centrifugation (13500 rpm for 5 minutes), and then redispersed in 1 mL of tertiary distilled water to obtain amine-functionalized DFNS / Au dot particles.
4mL 바이얼에서 아민 기능화된 DFNS/Au 나노입자의 DMF 현탁액(0.15mL)을 500rpm에서 15분 동안 교반하면서 아세트산 아연(0.50mL, 0.050M)의 DMF 용액과 혼합했다. 상기 혼합물에, [N3] 리간드(0.25mL, 0.050M) 및 2-MeIM(0.75mL, 0.050M)의 DMF 용액을 연속적으로 도입하였다. Zn2 +:[N3]:2-MeIM의 몰비는 2:1:3이다. 반응 혼합물을 500rpm에서 15분 동안 연속적으로 교반하였다. 그 후 80℃의 온도에서 8시간 동안 유지했다. 반응 완료 후, 얻은 생성물을 원심분리로 수집하고, DMF, 아세톤으로 수 회 세척한 다음, 진공하에 24시간 동안 건조하였다.A DMF suspension of amine functionalized DFNS / Au nanoparticles (0.15 mL) in a 4 mL vial was mixed with a DMF solution of zinc acetate (0.50 mL, 0.050 M) with stirring at 500 rpm for 15 minutes. To the mixture, a DMF solution of [N3] ligand (0.25 mL, 0.050M) and 2-MeIM (0.75mL, 0.050M) was continuously introduced. The molar ratio of Zn 2 + : [N3]: 2-MeIM is 2: 1: 3. The reaction mixture was stirred continuously at 500 rpm for 15 minutes. After that, it was kept at a temperature of 80 ° C. for 8 hours. After completion of the reaction, the obtained product was collected by centrifugation, washed several times with DMF and acetone, and then dried under vacuum for 24 hours.
실시예Example 9: 9: DFNSDFNS /Au@ZIF-8 나노입자 합성/ Au @ ZIF-8 nanoparticle synthesis
DFNS/Au@ZIF-8 나노입자는 DFNS/Au 나노입자와 DMF 용매 중 Zn2 +와 2-MeIM의 반응에 의해 합성된다. 전형적인 합성에서 아민 기능화된 DFNS/Au 나노입자의 메탄올 현탁액(0.3mL)을 500rpm에서 15분 동안 교반하면서 질산 아연(0.50mL, 0.050M)의 메탄올 용액과 혼합한다. 그 후, 메탄올 중 2-MeIM(1.00mL, 0.050M)을 Zn2 +:2-MeIM = 1:2의 몰비에 상응하게 투입한다. 반응 혼합물을 500rpm에서 15분 동안 연속적으로 교반하였다. 이후 실온에서 24시간 동안 유지했다. 생성물을 원심분리로 수집하고 메탄올, 아세톤으로 수 회 세척한 다음 24시간 동안 진공 건조하였다.DFNS / Au @ ZIF-8 nanoparticles are synthesized by the reaction of Zn 2 + and 2-MeIM of DFNS / Au nanoparticles and the solvent DMF. In a typical synthesis, a methanol suspension (0.3 mL) of amine functionalized DFNS / Au nanoparticles is mixed with a methanol solution of zinc nitrate (0.50 mL, 0.050 M) with stirring at 500 rpm for 15 minutes. Thereafter, 2-MeIM (1.00 mL, 0.050M) in methanol is added correspondingly to a molar ratio of Zn 2 + : 2-MeIM = 1: 2. The reaction mixture was stirred continuously at 500 rpm for 15 minutes. Then it was kept at room temperature for 24 hours. The product was collected by centrifugation, washed several times with methanol and acetone and then vacuum dried for 24 hours.
실시예Example 10: 10: 크노에베나겔Knoevenagel 축합반응( Condensation reaction ( KnoevenagelKnoevenagel Condensation) 촉매효과 분석 Condensation) catalytic effect analysis
형성된 혼성 나노물질 촉매를 사용한 벤즈알데하이드(benzaldehyde)와 말로노니트릴(malononitrile) 간의 크노에베나겔 축합 반응은 10mL의 1구 둥근 바닥 플라스크에서 수행된다. 1.00mL의 톨루엔이 들어있는 플라스크에 벤즈알데하이드(100μL, 0.98mmol)를 넣었다. 촉매 농도는 나노입자:벤즈알데하이드 몰비에 대해 계산된다. 반응 용기를 10분 동안 교반하여 촉매를 반응 용매에 분산시켰다. 이어서, 톨루엔(1.60mL) 중 말로노니트릴(129mg, 1.96mmol) 용액을 첨가하고, 이어서 반응 혼합물을 실온에서 5시간 동안 교반하였다. 벤즈알데하이드의 전환은 원심분리 후 가스 크로마토그래피로 분석하였다.The knoevenagel condensation reaction between benzaldehyde and malononitrile using the formed hybrid nanomaterial catalyst is performed in a 10 mL 1-neck round bottom flask. Benzaldehyde (100 μL, 0.98 mmol) was added to a flask containing 1.00 mL of toluene. The catalyst concentration is calculated relative to the nanoparticle: benzaldehyde molar ratio. The reaction vessel was stirred for 10 minutes to disperse the catalyst in the reaction solvent. Then, a solution of malononitrile (129 mg, 1.96 mmol) in toluene (1.60 mL) was added, and then the reaction mixture was stirred at room temperature for 5 hours. Conversion of benzaldehyde was analyzed by gas chromatography after centrifugation.
실시예Example 11: 특성 해석 11: Characteristic analysis
화합물의 적외선 분광(IR) 스펙트럼은 Nicolet iS5 FT-IR(ThermoScientific) 분광기 상에서 KBr 펠렛을 이용하여 400 - 4000cm-1 범위에서 기록하였다. 열중량분석(Thermogravimetric analyses; TGA)은 질소 분위기 하에서 가열속도 2℃/min으로 온도를 18℃에서 600℃까지 변화시켜가면서 TA Instruments SDT Q600 분석기를 이용하여 수행하였다. 분말 X선 회절(Powder X-ray diffraction; PXRD)은 RIGAKU Ultima IV 회절측정기를 사용하였으며, 10-80˚ 범위에서 Cu Kα 방사선(1.541Å)을 이용하여 연속 스캔속도 2°/min의 초점 빔 배치(focused beam configuration) 상태에서 측정하였다. 가상 PXRD 패턴은 Mercury 3.3 프로그램을 이용하여 단일결정 X선 회절로부터 계산하였다. 나노 입자는 Hitachi S-4800 주사전자현미경(scanning electron microscopy; SEM)과 JEOL JEM-2010 Luminography(Fuji FDL-5000) Ultramicrotome(CRX) 투과전자현미경(transmission electron microscopy; TEM)을 이용해 촬영하였다. 고해상도 투과 전자 현미경(High-resolution transmission electron microscopy; HRTEM) 분석과 에너지 분산형 X-ray(EDX)와 선택적 전자회절(selected-area electron diffraction; SAED) 패턴 분석은 JEOL JEM-2100F 투과전자현미경을 이용하여 측정하였다. TEM용 시료는 원심분리(3회, 2분 30초, 9000rpm)를 이용하여 나노입자 혼합물을 농축하고, 이후 에탄올(200㎕)에 재현탁하고 이 용액의 일부인 10㎕를 TEM 그리드(Ted Pella, Inc. Formvar/Carbon 400 mesh, 구리 코팅)에 고정하여 제조하였다. N2 흡착 등온선은 BELSORP-mini II(BEL Japan, Inc.)를 이용하여 얻었다. 흡착 실험 동안 사용한 기체는 순도가 높은 것이었다(99.999%). 모든 시료는 DMF(3 × 1㎖) 및 아세톤(3 × 1㎖)으로 충분히 헹군 다음, 기체 흡착실험에 앞서 24시간 동안 진공 하에서 건조하여 활성화하였다. 자외선-가시광선 스펙트럼은 UV-1800(Shimadzu, UV-vis spectrophotometer)으로 측정하였다. 용액의 pH는 Orion 420 A+ pHmeter를 사용하여 측정하였다. The infrared spectral (IR) spectrum of the compound was recorded in the range of 400-4000 cm -1 using KBr pellets on a Nicolet iS5 FT-IR (ThermoScientific) spectrometer. Thermogravimetric analysis (TGA) was performed using a TA Instruments SDT Q600 analyzer while changing the temperature from 18 ° C to 600 ° C at a heating rate of 2 ° C / min under a nitrogen atmosphere. For powder X-ray diffraction (PXRD), a RIGAKU Ultima IV diffractometer was used, and the focus beam was placed at a continuous scan speed of 2 ° / min using Cu Kα radiation (1.541 Å) in the range of 10-80 °. It was measured in the (focused beam configuration) state. Virtual PXRD patterns were calculated from single crystal X-ray diffraction using the Mercury 3.3 program. Nanoparticles were taken using a Hitachi S-4800 scanning electron microscopy (SEM) and JEOL JEM-2010 Luminography (Fuji FDL-5000) Ultramicrotome (CRX) transmission electron microscopy (TEM). High-resolution transmission electron microscopy (HRTEM) analysis and energy dispersive X-ray (EDX) and selective-area electron diffraction (SAED) pattern analysis are performed using JEOL JEM-2100F transmission electron microscope. Was measured. For the TEM sample, the nanoparticle mixture was concentrated using centrifugation (3 times, 2
결과 및 토의Results and discussion
돌기 섬유질형 나노실리카(Dendritic Fibrous Nanosilica, "DFNS")의 합성은 종래 보고된 비슷한 형태의 나노구조체 합성법을 변형하여 합성하였다(1,7). DFNS 입자 형성에서 사용된 계면활성제인 CTAB는, 다중 가지(주름) 형성의 주형(template)으로 중요한 작용을 하게 된다. 실리카 전구체인 TEOS는 요소에 의해서 가수분해되어 음전하를 띄는 실리케이트 분자들을 형성하고 응집되어 있는 CTAB 분자들 사이에서 방사형의 방향으로 자가조립(self-assembly)을 하게 되며, 조립된 형태로 축합 반응이 일어나면서 섬유질 형태를 띠는 실리카 나노입자가 형성된다. 합성된 DFNS는 550℃의 고온 조건에서 6시간 동안 하소(calcination)하는데, 이 단계에서 입자에 남아있는 유기물과 계면활성제(CTAB)를 제거하게 된다. 형성된 DFNS는 구형인 실리카 표면에 매우 많은 돌기 섬유형의 주름을 보이며 매우 큰 표면적을 지니게 된다. Synthesis of dendritic fibrous nanosilica (“DFNS”) was synthesized by modifying a similar method of synthesizing nanostructures reported previously (1,7). CTAB, a surfactant used in the formation of DFNS particles, plays an important role as a template for multiple branch (wrinkle) formation. TEOS, a silica precursor, is hydrolyzed by urea to form negatively charged silicate molecules and self-assembly in the radial direction between aggregated CTAB molecules, and condensation reaction occurs in an assembled form. While the silica nanoparticles having a fibrous form are formed. The synthesized DFNS is calcined for 6 hours at a high temperature of 550 ° C., and at this stage, the organic matter and surfactant (CTAB) remaining on the particles are removed. The formed DFNS shows a very large number of protrusion fibrous wrinkles on the spherical silica surface and has a very large surface area.
다양한 형태의 Au 입자를 DFNS에 형성(DFNS/Au 나노입자)하는 합성은 종래 보고된 합성법을 이용하였다(7). 이는 시드 매개법으로 DFNS 표면에 Au 나노닷을 형성하여(DFNS/Au dot 입자) 이를 시드로 이용하여 추가적인 금 물질을 형성하는 방식이다. DFNS/Au 나노입자의 합성은 우선 아민 기능화(amine functionalization) 단계를 진행한 이후 Au 이온을 직접 환원하는 방식(in situ reduction)으로 수행하였다. DFNS 표면의 하이드록시기(-OH)를 아민기(-NH2)로 변환하고, 금 이온(Au3 +)이 아민기(-NH2)가 붙어있는 실리카 표면에 쉽게 접근할 수 있는 환경을 만들어준 다음, NaBH4를 사용하여 금 이온을 환원하였다.Synthesis of forming various types of Au particles in DFNS (DFNS / Au nanoparticles) was performed using a previously reported synthesis method (7). This is a method of forming an Au nanodot on the surface of the DFNS (DFNS / Au dot particles) by a seed mediating method to form an additional gold material using it as a seed. Synthesis of DFNS / Au nanoparticles was performed by in situ reduction after first performing an amine functionalization step and then directly reducing Au ions. The hydroxy group (-OH) on the surface of DFNS is converted to an amine group (-NH 2 ), and an environment in which gold ions (Au 3 + ) can easily access the silica surface with an amine group (-NH 2 ) After making it, NaBH 4 was used to reduce gold ions.
돌기 섬유질형 나노실리카 코어-Zn 기반 배위 고분자 쉘 나노입자 (DFNS@ZIF-8 또는 DFNS@Zn_CPN 나노입자)는 기 형성된 DFNS 나노입자의 표면에서 Zn 기반 배위 고분자를 형성하는 방식으로 진행되었다. 우리는 Zn 이온과 2-메틸이미다졸(2-MeIM)을 이용해 합성할 수 있는 금속-유기 구조체(ZIF-8)의 합성법을 이용하여 배위 고분자를 합성하였다. 또한, Zn 이온과 2-메틸이미다졸(2-MeIM)을 이용해 배위 고분자를 합성할 때 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 ({2,6-bis[(4-carboxyanilino)carbonyl]pyridine}, [N3] 리간드)을 추가하여 합성되는 배위 고분자(Zn_CPN)를 이용하였다. 합성 과정에서는 특히 DFNS 표면의 하이드록시기(-OH)를 아민기(-NH2)로 바꾸는 표면 개질을 위하여 APTES를 가하여 반응시켰다(DFNS-NH2). DFNS의 표면을 아민기로 개질하는 과정은 선택적으로 DFNS의 표면에서만 Zn 기반 배위 고분자들이 형성되도록 하는데 중요하다.The protruding fibrous nanosilica core-Zn-based coordination polymer shell nanoparticles (DFNS @ ZIF-8 or DFNS @ Zn_CPN nanoparticles) were performed by forming a Zn-based coordination polymer on the surface of previously formed DFNS nanoparticles. We synthesized the coordination polymer using a synthesis method of a metal-organic structure (ZIF-8) that can be synthesized using Zn ion and 2-methylimidazole (2-MeIM). Also, when synthesizing a coordination polymer using Zn ion and 2-methylimidazole (2-MeIM), 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine ({2,6-bis [( Coordination polymer (Zn_CPN) synthesized by adding 4-carboxyanilino) carbonyl] pyridine}, [N3] ligand) was used. Synthesis process, in particular for the surface modification changes the hydroxy group (-OH) of the surface DFNS to an amine group (-NH 2) was added to the reaction APTES (DFNS-NH 2). The process of modifying the surface of DFNS with an amine group is important to selectively form Zn-based coordination polymers only on the surface of DFNS.
도 1은 DFNS@Zn_CPN 나노입자의 합성반응식과 형성된 나노입자의 전자현미경 이미지이다. Zn2 +를 제공하기 위해 Zn(OAC)2가 사용되었으며 2-MeIM과 더불어 [N3] 리간드를 함께 반응시켰다. 이 과정에서 [N3] 리간드의 용해를 위해 용매로 DMF를 이용하였다. 이용된 Zn2 +:[N3]:2-MeIM의 몰비는 2:1:3이다. 도 1(a), (b)는 DFNS@Zn_CPN 나노입자의 주사전자현미경(SEM) 이미지이며 도 1(c), (d)는 DFNS@Zn_CPN 나노입자의 투과전자현미경(TEM) 이미지이다. 형성된 나노입자는 울퉁불퉁한 표면을 지니고 있으며, 크기는 직경이 대략 589±66nm(121개의 입자를 분석함)이다. 코어로 이용된 DFNS의 평균 직경이 528±52nm(121개의 입자를 분석함)이므로 쉘로 형성된 Zn_CPN의 두께는 약 30nm이다. 특히, 도 1(c), (d)에서 확인되듯이 DFNS의 돌기 섬유형 표면 구조는 Zn_CPN이 표면에 형성되어도 전혀 영향을 받지 않는다. 아울러 DFNS와 Zn_CPN 사이에 빈 공간이 형성되어 있음을 명확히 볼 수 있다. 도 1(d)는 DFNS@Zn_CPN 나노입자의 EDS(energy dispersive x-ray spectroscopy) 맵핑 분석 결과이다. 분석 결과 DFNS/Au 닷 입자에 N, Si,C, O, Zn 원소가 모두 존재하는 것을 확인할 수 있다. 특히, DFNS@Zn_CPN 나노입자의 전체적인 분포에서 Si는 내부에, Zn은 외곽에 분포되어 있음을 명확히 알 수 있다. 이러한 구조적 특징은 코어-쉘 구조의 DFNS@Zn_CPN 나노입자가 성공적으로 합성되었음을 말해준다.1 is an electron microscope image of the synthesis reaction formula and formed nanoparticles of DFNS @ Zn_CPN nanoparticles. Zn (OAC) to provide the Zn 2 + 2 was used and reacted with the [N3] ligand, with 2-MeIM. In this process, DMF was used as a solvent for the dissolution of the [N3] ligand. The molar ratio of Zn 2 + : [N3]: 2-MeIM used is 2: 1: 3. 1 (a) and (b) are scanning electron microscope (SEM) images of DFNS @ Zn_CPN nanoparticles, and FIGS. 1 (c) and (d) are transmission electron microscope (TEM) images of DFNS @ Zn_CPN nanoparticles. The formed nanoparticles have an uneven surface, and the size is approximately 589 ± 66 nm in diameter (analyzing 121 particles). Since the average diameter of DFNS used as a core is 528 ± 52 nm (121 particles are analyzed), the thickness of Zn_CPN formed by the shell is about 30 nm. In particular, as shown in Figs. 1 (c) and (d), the protruding fibrous surface structure of DFNS is not affected at all even when Zn_CPN is formed on the surface. In addition, it can be clearly seen that an empty space is formed between DFNS and Zn_CPN. FIG. 1 (d) shows the results of energy dispersive x-ray spectroscopy (EDS) mapping analysis of DFNS @ Zn_CPN nanoparticles. As a result of the analysis, it can be confirmed that N, Si, C, O, and Zn elements are all present in the DFNS / Au dot particles. In particular, it can be clearly seen that in the overall distribution of DFNS @ Zn_CPN nanoparticles, Si is distributed inside and Zn is distributed outside. These structural characteristics indicate that the DFNS @ Zn_CPN nanoparticles of the core-shell structure were successfully synthesized.
도 2는 DFNS와 Zn_CPN(DFNS를 가하지 않고 2:1:3의 몰비로 Zn2 +, [N3], 2-MeIM을 가하여 형성한 배위 고분자 나노구조체) 그리고 DFNS@Zn_CPN 나노입자의 분석 결과이다. 도 2(a)는 각 나노입자의 분말 X선 회절(Powder X-ray diffraction; PXRD) 측정 결과이다. 나노실리카(DFNS)는 특별한 결정성을 보이지 않지만 Zn_CPN과 DFNS@Zn_CPN 나노입자는 배위 고분자에 기인한 동일한 결정성을 보임을 알 수 있다. 이 나노입자들의 PXRD 패턴은 ZIF-8의 시뮬레이션 패턴(CCDC 602542)과 상당히 유사하다. 도 2(b)는 77K에서 측정한 각 나노입자의 N2 흡착 등온선을 보여준다. 상대적 압력이 낮은 상태에서 흡착의 증가는 미세공극의 존재로 인한 것인 반면, 상대적 압력이 높은 상태에서 이력 현상은 구조상 메조공극 또는 큰 공극의 존재를 말해주는데, 이것은 나노입자의 특이한 적층 결과이다. DFNS@Zn_CPN 나노입자의 BET 표면적은 521m2g-1로 나타났고, 이는 Zn_CPN의 BET 표면적(1808m2g-1)보다 낮다. 도 2(c)는 적외선 분광 측정결과(FTIR (Fourier-transform infrared))이며 DFNS@Zn_CPN의 FTIR 스펙트럼 또한 유리 리간드 [N3]에 대하여 C=Ocarboxylate 스트레칭이 이동하였음을 보여준다. 또한, [N3]에 기인한 C=N 스트레칭이 명확히 관측된다. Zn_CPN은 각각의 리간드에서 보일 수 있는 스펙트럼이 관측되나 실리카의 넓은 스펙트럼이 DFNS@Zn_CPN 나노입자에서 겹쳐 나옴을 확인할 수 있다. 도 2(d)는 자외선-가시광선 (UV-vis) 흡광도 분석 결과이다. DFNS는 어떤 흡광도도 300nm 이상의 파장에서 보이지 않으나 DFNS@Zn_CPN 와 Zn_CPN 나노입자의 경우 약 320nm 영역에서 Zn 기반 배위 고분자에 기인한 흡광도를 관측할 수 있다.Figure 2 is a DFNS and Zn_CPN (Zn 2 + , with a molar ratio of 2: 1: 3 without adding DFNS, [N3], a coordinate polymer nanostructure formed by adding 2-MeIM) and DFNS @ Zn_CPN nanoparticles. Figure 2 (a) is a powder X-ray diffraction (PXRD) measurement results of each nanoparticle. Nanosilica (DFNS) shows no special crystallinity, but Zn_CPN and DFNS @ Zn_CPN nanoparticles show the same crystallinity due to the coordination polymer. The PXRD pattern of these nanoparticles is quite similar to the simulation pattern of ZIF-8 (CCDC 602542). 2 (b) shows the N 2 adsorption isotherm of each nanoparticle measured at 77K. While the increase in adsorption at low relative pressure is due to the presence of micropores, the hysteresis at high relative pressures indicates the presence of mesopores or large pores in structure, which is a result of the unusual deposition of nanoparticles. The BET surface area of DFNS @ Zn_CPN nanoparticles was 521 m 2 g -1 , which was lower than the BET surface area of Zn_CPN (1808 m 2 g -1 ). FIG. 2 (c) shows the results of infrared spectroscopy (Fourier-transform infrared (FTIR)) and the FTIR spectrum of DFNS @ Zn_CPN also shows that the C = O carboxylate stretching shifted with respect to the free ligand [N3]. In addition, C = N stretching due to [N3] is clearly observed. As for Zn_CPN, a spectrum that can be seen in each ligand is observed, but it can be confirmed that the broad spectrum of silica overlaps with DFNS @ Zn_CPN nanoparticles. 2 (d) shows the results of ultraviolet-visible (UV-vis) absorbance analysis. DFNS does not show any absorbance at wavelengths above 300nm, but for DFNS @ Zn_CPN and Zn_CPN nanoparticles, it is possible to observe the absorbance due to the Zn-based coordination polymer in the region of about 320nm.
DFNS@Zn_CPN 나노입자의 배위 고분자 층의 두께는 일차적으로 배위 고분자 쉘을 형성하기 위해 가해준 반응물과 반응시간(15분 반응, 8시간 동안 80℃에서 유지)을 한 사이클로 했을 때 이를 반복적으로 시행하여 변화시킬 수 있다. 각 사이클에서 DFNS@Zn_CPN의 DMF 현탁액은 최신 DFNS@Zn_CPN을 DMF 0.15mL에 분산시킴으로써 얻어지지만, 다른 실험 조건은 변함없이 유지된다. 도 3은 반복적인 사이클에 의해 형성된 DFNS@Zn_CPN 나노입자의 SEM 이미지와 각각의 직경을 측정한 히스토그램이다. 각각의 경우에 평균 직경은 1 cycle: 589±66nm (178개 입자를 측정함), 2 cycle : 646±49nm (169개의 입자를 측정함), 3 cycle : 667±44nm (97개의 입자를 측정함), 4 cycle : 719±76nm(152개의 입자를 측정함), 5 cycle : 819±42nm (130개의 입자를 측정함)이다. 반복적인 배위 고분자 합성을 기 형성된 혼성 나노입자 상에서 진행함으로써 DFNS@Zn_CPN 나노입자의 전체적인 크기와 Zn_CPN 층의 두께를 쉽게 조절할 수 있다.The thickness of the coordination polymer layer of DFNS @ Zn_CPN nanoparticles is performed repeatedly when the reactant and reaction time (15 minutes reaction, maintained at 80 ° C. for 8 hours) applied to form the coordination polymer shell are performed as one cycle. Can be changed. The DMF suspension of DFNS @ Zn_CPN in each cycle was obtained by dispersing the latest DFNS @ Zn_CPN in 0.15 mL of DMF, but other experimental conditions remained unchanged. 3 is a histogram of SEM images and diameters of DFNS @ Zn_CPN nanoparticles formed by repetitive cycles. In each case, the average diameter was 1 cycle: 589 ± 66nm (measured 178 particles), 2 cycles: 646 ± 49nm (measured 169 particles), 3 cycles: 667 ± 44nm (measured 97 particles) ), 4 cycles: 719 ± 76nm (measured 152 particles), 5 cycles: 819 ± 42nm (measured 130 particles). It is possible to easily adjust the overall size of the DFNS @ Zn_CPN nanoparticles and the thickness of the Zn_CPN layer by performing the repetitive coordination polymer synthesis on preformed hybrid nanoparticles.
DFNS 코어에 쉘로 [N3] 리간드를 가하지 않고 Zn 이온과 2-메틸이미다졸(2-MeIM)을 반응시켜 ZIF-8 형태의 배위 고분자(DFNS/ZIF-8 나노입자)를 용이하게 형성할 수 있다. DFNS를 우선적으로 아민 기능화시킨 후 메탄올에 현탁하고 이후 Zn 이온과 2-MeIM을 가하여 메탄올 상에서 반응시켰다. 도 4(a), (b)는 형성된 DFNS/ZIF-8 나노입자의 SEM 이미지이다. 이 이미지에서 각이 진 형태의 개별 입자들이 뭉쳐서 만들어진 형태로 ZIF-8층이 보이며, 이를 통해 각각의 ZIF-8 배위 고분자 나노구조체가 DFNS의 표면에서 개별적으로 성장함을 알 수 있다. DFNS@ZIF-8의 크기는 직경이 대략 588±40nm (142개의 입자를 측정함)이다. 이는 DFNS@Zn_CPN(589±66nm)과 매우 유사하다. 이 ZIF-8층의 결정성은 PXRD 실험을 통해 확인할 수 있으며(도 4(c)), DFNS 없이 형성된 ZIF-8의 PXRD 패턴과 거의 동일하게 관측됨을 알 수 있다. 또한, 이 패턴은 ZIF-8의 시뮬레이션 패턴(CCDC 602542)과 상당히 유사하다.Without adding a [N3] ligand as a shell to the DFNS core, Zn ions and 2-methylimidazole (2-MeIM) can be reacted to easily form a coordination polymer (DFNS / ZIF-8 nanoparticle) in the form of ZIF-8. have. DFNS was preferentially amine functionalized, then suspended in methanol, and then reacted on methanol by adding Zn ion and 2-MeIM. 4 (a) and (b) are SEM images of the formed DFNS / ZIF-8 nanoparticles. In this image, the ZIF-8 layer can be seen in the form of individual particles in the form of agglomeration, and it can be seen that each ZIF-8 coordinating polymer nanostructure grows individually on the surface of the DFNS. The size of DFNS @ ZIF-8 is approximately 588 ± 40 nm in diameter (measures 142 particles). This is very similar to DFNS @ Zn_CPN (589 ± 66nm). The crystallinity of this ZIF-8 layer can be confirmed through a PXRD experiment (FIG. 4 (c)), and it can be seen that it is observed almost the same as the PXRD pattern of ZIF-8 formed without DFNS. In addition, this pattern is quite similar to the simulation pattern of ZIF-8 (CCDC 602542).
다양한 크기의 Au 나노입자를 DFNS 표면에서 형성하기 위해선 DFNS를 아민 기능화한 후 Au dot을 우선적으로 DFNS에 형성한다(DFNS/Au dot 입자). 이는 이후 추가적으로 HAuCl4를 가하여 Au 나노입자를 형성하는 시드로 이용될 수 있다. DFNS/Au 나노입자를 형성하기 전, 시드로 이용되는 DFNS/Au dot 입자를 코어로 하여 Zn 기반 배위 고분자 쉘의 합성을 시도하였다(DFNS/Au dot@Zn_CPN 나노입자). 배위 고분자 합성을 위해 DFNS/Au dot 입자는 아민기로 기능화하고 DMF에 현탁하였다. Zn_CPN 쉘을 형성하기 위해 이용된 Zn2 +:[N3]:2-MeIM의 몰비는 2:1:3이다. 도 5는 DFNS/Au dot@Zn_CPN 나노입자를 합성하는 반응식과 형성된 입자의 전자현미경 이미지를 나타내었다. 도 5(a)는 DFNS/Au dot@Zn_CPN 나노입자의 SEM 이미지이다. 전체적으로 균일한 크기와 형태를 보이는 입자가 높은 수율로 형성됨을 알 수 있다. 특히 각이 진 쉘의 형태를 보이며 배위 고분자 나노입자가 개별적으로 결정화되는 것을 예측할 수 있다. 도 5(b)는 합성된 나노입자의 직경을 측정한 히스토그램이다. 합성된 입자의 평균 직경은 678±51nm였다. 도 5(c)는 TEM 이미지이며 코어인 DFNS의 돌기 섬유형 구조가 명확히 구분된다. DFNS@Zn_CPN 나노입자와 마찬가지로 배위 고분자 형성시 DFNS의 구조적 특성이 전혀 무너지지 않음을 알 수 있다. Au dot은 그 크기가 매우 작아 TEM 이미지 상에서는 그 존재 여부를 확인하기 어려우나 EDS 맵핑 분석 결과, 코어 DFNS 주변과 Zn_CPN 층의 내부에 전체적으로 분포되어 있음을 명확히 알 수 있다. In order to form Au nanoparticles of various sizes on the surface of DFNS, DFNS is amine-functionalized and Au dots are preferentially formed in DFNS (DFNS / Au dot particles). This can then be used as a seed to form Au nanoparticles by additionally adding HAuCl 4 . Before forming DFNS / Au nanoparticles, synthesis of a Zn-based coordination polymer shell was attempted using DFNS / Au dot particles used as seeds as cores (DFNS / Au dot @ Zn_CPN nanoparticles). For coordination polymer synthesis, DFNS / Au dot particles were functionalized with amine groups and suspended in DMF. The molar ratio of Zn 2 + : [N3]: 2-MeIM used to form the Zn_CPN shell is 2: 1: 3. 5 shows a reaction formula for synthesizing DFNS / Au dot @ Zn_CPN nanoparticles and an electron microscope image of the formed particles. 5 (a) is an SEM image of DFNS / Au dot @ Zn_CPN nanoparticles. It can be seen that the particles having uniform size and shape as a whole are formed in a high yield. In particular, it is possible to predict that the coordinated polymer nanoparticles are crystallized individually, showing the shape of an angled shell. Figure 5 (b) is a histogram measuring the diameter of the synthesized nanoparticles. The average diameter of the synthesized particles was 678 ± 51 nm. 5 (c) is a TEM image, and the protruding fibrous structure of the core DFNS is clearly distinguished. As with DFNS @ Zn_CPN nanoparticles, it can be seen that the structural properties of DFNS do not collapse at all when the coordination polymer is formed. The size of Au dot is very small, so it is difficult to confirm its existence on the TEM image. As a result of EDS mapping analysis, it can be clearly seen that it is entirely distributed around the core DFNS and inside the Zn_CPN layer.
도 6은 DFNS/Au dot@Zn_CPN 나노입자의 PXRD(a), BET(b), IR(c), 흡광도(d) 측정 결과이다. 전체적인 분광학적 경향은 DFNS@Zn_CPN를 측정한 결과와 크게 차이가 나지 않으며 BET 표면적은 929m2g-1이다.6 is a result of measuring PXRD (a), BET (b), IR (c), and absorbance (d) of DFNS / Au dot @ Zn_CPN nanoparticles. The overall spectroscopic trend is not significantly different from the result of measuring DFNS @ Zn_CPN, and the BET surface area is 929 m 2 g -1 .
DFNS/Au dot을 시드로 하여 Au 입자를 형성한 DFNS/Au 나노입자를 코어로 이용하고 Zn 기반 배위 고분자를 형성할 경우 DFNS/Au dot@Zn_CPN 나노입자와는 그 형태에서 차이를 보인다. 도 7은 DFNS/Au@Zn_CPN 나노입자의 합성반응식과 형성된 나노입자의 전자현미경 이미지이다. 도 7(a)는 SEM 이미지이며 코어인 DFNS/Au 나노입자의 존재가 명확히 보인다. 이는 금 성분이 DFNS/Au dot@Zn_CPN 나노입자의 경우보다 많으면서 다른 성분의 물질과 차이가 분명히 드러나기 때문이다. 특히 Zn_CPN이 DFNS/Au dot@Zn_CPN 나노입자와 다르게 비교적 균일하게 형성됨을 알 수 있다. 이는 DFNS나 DFNS/Au dot 입자에 직접적으로 배위 고분자가 형성될 경우 그 표면이 돌기 섬유형으로 이루어져 있어 매우 불규칙적이므로 다중의 결정이 형성되는 것이 더욱 우세하게 되지만, DFNS/Au 나노입자의 경우 DFNS의 표면이 전체적으로 Au 나노입자들에 의해 덮이게 되면서 상대적으로 표면의 불규칙성이 완화되기 때문이다. 이 경우에는 좀 더 균일한 배위 고분자 결정이 형성될 가능성이 높아진다. 그 형태적 특성은 TEM 이미지에서 좀 더 명확하게 확인할 수 있다(도 7(c)). Au 나노입자의 존재는 이 이미지에서 분명하게 확인 가능하다. 도 7(b)는 합성된 나노입자의 직경을 측정한 히스토그램이다. 합성된 입자의 평균 직경은 1180±80nm였다. EDS 맵핑 분석 결과, 코어 DFNS 주변에서, Zn_CPN 층의 내부에 Au의 존재를 좀 더 분명히 확인할 수 있다.When DFNS / Au dot is used as a seed to form Au particles as DFNS / Au nanoparticles as a core, and when forming a Zn-based coordination polymer, there is a difference in form from DFNS / Au dot @ Zn_CPN nanoparticles. 7 is an electron microscope image of the nanoparticles and the synthetic reaction formula of DFNS / Au @ Zn_CPN nanoparticles. 7 (a) is an SEM image and the presence of the core DFNS / Au nanoparticles is clearly seen. This is because the gold component is more than that of the DFNS / Au dot @ Zn_CPN nanoparticles, and the difference from other components is clearly revealed. In particular, it can be seen that Zn_CPN is formed relatively uniformly unlike DFNS / Au dot @ Zn_CPN nanoparticles. This is because when the coordination polymer is directly formed on the DFNS or DFNS / Au dot particles, the surface is made of protruding fibers and is very irregular, so it is more prevalent to form multiple crystals, but in the case of DFNS / Au nanoparticles, This is because irregularity of the surface is relatively alleviated as the surface is entirely covered by Au nanoparticles. In this case, the possibility of forming a more uniform coordination polymer crystal increases. The morphological characteristics can be confirmed more clearly in the TEM image (Fig. 7 (c)). The presence of Au nanoparticles can be clearly seen in this image. 7 (b) is a histogram measuring the diameter of the synthesized nanoparticles. The average diameter of the synthesized particles was 1180 ± 80nm. As a result of the EDS mapping analysis, it is possible to more clearly confirm the presence of Au in the Zn_CPN layer around the core DFNS.
도 8(a)에서 알 수 있듯이, DFNS/Au@Zn_CPN의 PXRD 패턴은 5 ~ 35˚ 범위의 Zn_CPN 피크와 35 ~ 90˚ 범위의 금(Au) 피크를 생성한다(JCPDS card no. 01-089-3697). DFNS/Au@Zn_CPN의 BET 표면적은 1103m2g-1이며, 도 8(b)를 통해 원래의 DFNS/Au dot@Zn_CPN보다 기공의 크기가 약간 크다는 것을 알 수 있다.As can be seen in FIG. 8 (a), the PXRD pattern of DFNS / Au @ Zn_CPN generates a Zn_CPN peak in the range of 5 to 35 ° and a gold (Au) peak in the range of 35 to 90 ° (JCPDS card no. 01-089 -3697). The BET surface area of DFNS / Au @ Zn_CPN is 1103 m 2 g -1 , and it can be seen from FIG. 8 (b) that the pore size is slightly larger than the original DFNS / Au dot @ Zn_CPN.
합성된 DFNS/Au 나노입자의 메탄올 용액에서 질산 아연과 2-MeIM 리간드를 반응시켜 DFNS/Au@ZIF-8을 용이하게 형성할 수 있다. 도 9는 DFNS/Au@ZIF-8 나노입자의 주사전자현미경(SEM) 이미지이다. 입자가 완전히 균일하지는 않더라도 성공적으로 제조된 코어-쉘 구조의 DFNS/Au@ZIF-8 나노입자를 얻을 수 있었다. 형성된 DFNS/Au@ZIF-8 입자의 평균 크기는 1146±102nm(128개의 입자를 측정함)이다.DFNS / Au @ ZIF-8 can be easily formed by reacting zinc nitrate with a 2-MeIM ligand in a methanol solution of synthesized DFNS / Au nanoparticles. 9 is a scanning electron microscope (SEM) image of DFNS / Au @ ZIF-8 nanoparticles. Even if the particles were not completely uniform, DFNS / Au @ ZIF-8 nanoparticles having a successfully prepared core-shell structure could be obtained. The average size of DFNS / Au @ ZIF-8 particles formed is 1146 ± 102 nm (128 particles are measured).
본 발명에서 합성된 하이브리드 재료의 촉매 활성을 시험하기 위해, 톨루엔 용액에서 벤즈알데하이드(benzaldehyde)와 말로노니트릴(malononitrile) 간의 크노에베나겔 축합(Knoevenagel Condensation) 반응을 진행하였다. 반응 후 벤즈알데하이드의 전환율은 톨루엔 용액의 벤즈알데하이드의 검량선을 기반으로 계산된다(도 10). DFNS/Au 나노입자, DFNS/Au@ZIF-8 나노입자, DFNS/Au@Zn_CPN 나노입자를 이용하여 크노에베나겔 축합반응의 촉매효과를 비교하였다. 촉매로 이용된 나노입자의 양은 동일하게 가하였다(DFNS 나노입자 합성에 이용된 TEOS의 몰수와 배위 고분자 쉘 형성에 이용된 시약들의 양은 각각의 경우에 동일함). 도 11은 이 세 나노입자를 이용한 촉매효과를 비교한 그래프이다. DFNS/Au 나노입자를 이용할 경우 벤즈알데히드의 전환이 거의 이루어지지 않았으며, 이를 통해 Au나 DFNS는 이 반응에서 촉매효과가 없는 것으로 생각된다. 그러나 DFNS/Au@Zn_CPN 나노입자를 이용할 경우 72% 의 매우 높은 전환율을 보였으며 이를 통해 DFNS/Au@Zn_CPN 나노입자의 촉매로서의 이용가능성이 매우 큼을 알 수 있다. 흥미롭게도 DFNS/Au@Zn_CPN 나노입자의 촉매효과는 DFNS/Au@ZIF-8 나노입자의 촉매효과(35%)보다 높으며, 이는 DFNS/Au@Zn_CPN의 높은 표면적과, [N3] 리간드의 존재로 인해 Zn2 +가 배위되어 형성된 추가적인 촉매활성부분이 촉매효과의 증가에 영향을 미치는 것으로 여겨진다. 아울러 DFNS/Au 나노입자의 돌기 섬유형 표면에 기인한 구조적 특성은 쉘로 이루어진 Zn 기반의 배위 고분자의 촉매작용에 기하학적 이점을 제공할 수 있다.In order to test the catalytic activity of the hybrid material synthesized in the present invention, a Knoevenagel Condensation reaction between benzaldehyde and malononitrile was performed in a toluene solution. The conversion of benzaldehyde after the reaction is calculated based on the calibration curve of benzaldehyde in the toluene solution (FIG. 10). The catalytic effect of the Knoevenagel condensation reaction was compared using DFNS / Au nanoparticles, DFNS / Au @ ZIF-8 nanoparticles, and DFNS / Au @ Zn_CPN nanoparticles. The amount of nanoparticles used as a catalyst was added in the same manner (the number of moles of TEOS used for synthesizing DFNS nanoparticles and the amount of reagents used to form a coordinated polymer shell were the same in each case). 11 is a graph comparing the catalytic effect using these three nanoparticles. When DFNS / Au nanoparticles were used, conversion of benzaldehyde was hardly achieved, and it is believed that Au or DFNS has no catalytic effect in this reaction. However, when the DFNS / Au @ Zn_CPN nanoparticles were used, it showed a very high conversion rate of 72%, indicating that the availability of the DFNS / Au @ Zn_CPN nanoparticles as a catalyst was very high. Interestingly, the catalytic effect of DFNS / Au @ Zn_CPN nanoparticles is higher than that of DFNS / Au @ ZIF-8 nanoparticles (35%), which is due to the high surface area of DFNS / Au @ Zn_CPN and the presence of [N3] ligand. due believed that additional catalytically active portion formed a Zn 2 + is coordinated affects the increase in the catalytic activity. In addition, structural properties due to the protruding fibrous surface of the DFNS / Au nanoparticles can provide geometrical advantages for the catalysis of Zn-based coordination polymers composed of shells.
Claims (17)
상기 코어의 외주면에 형성되며, 두께는 30~1000nm이며, DMF 용액에서 2-메틸이미다졸 및 Zn2 +의 반응에 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 {2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가하여 형성한 Zn 기반 배위 고분자 쉘을 포함하는 나노입자.
Protruding fibrous nano-silica core with a particle size of 200 ~ 600nm and
It is formed on the outer peripheral surface of the core, a thickness of 30 ~ 1000nm, and the reaction of the 2,6-bis 2-methylimidazole and Zn 2 + in a DMF solution [(4-carboxy-anilino) carbonyl] pyridin-2 { , 6-bis [(4-carboxyanilino) carbonyl] pyridine} nanoparticles comprising a Zn-based coordination polymer shell formed by adding a ligand.
상기 돌기 섬유질형 나노실리카 코어와 Zn 기반 배위 고분자 쉘 사이에 공간이 존재함을 특징으로 하는 나노입자.
The method according to claim 1,
Nanoparticles characterized in that there is a space between the projection fibrous nanosilica core and the Zn-based coordination polymer shell.
상기 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 리간드는 농도 0.01M 내지 0.05M로 가함을 특징으로 하는 나노입자.
The method according to claim 1,
The 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine ligand is a nanoparticle, characterized in that added at a concentration of 0.01M to 0.05M.
상기 Zn2 + : 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 : 2-메틸이미다졸의 몰비는 2:1:3 ~ 2:2:3임을 특징으로 하는 나노입자.
The method according to claim 1,
The Zn 2 +: 2,6- bis [(4-carboxy-anilino) carbonyl] pyridine: 2-Methyl imidazole is the molar ratio of 2: nano-particles characterized in that the 3: 1: 3 ~ 2: 2.
상기 코어의 외주면에 형성되며 두께 30~1000nm인 Zn 기반 배위 고분자 ZIF-8 쉘을 포함하는 나노입자.
Protruding fibrous nano-silica core with a particle size of 200 ~ 600nm and
Nanoparticles formed on the outer circumferential surface of the core and including a Zn-based coordination polymer ZIF-8 shell having a thickness of 30 to 1000 nm.
상기 Zn2 + : 2-메틸이미다졸의 몰비는 1:2임을 특징으로 하는 나노입자.
The method according to claim 5,
Nanoparticles, characterized in that the molar ratio of the Zn 2 + : 2-methylimidazole is 1: 2.
상기 돌기 섬유질형 나노실리카 코어와 Zn 기반 배위 고분자 ZIF-8 쉘 사이에 공간이 존재함을 특징으로 하는 나노입자.
The method according to claim 5,
Nanoparticles characterized in that there is a space between the projection fibrous nanosilica core and Zn-based coordination polymer ZIF-8 shell.
돌기 섬유질형 나노실리카 코어의 메탄올 용액에 2-메틸이미다졸 및 Zn2 +를 가하는 반응을 2회 이상 실시하여 생성되는 나노입자의 크기를 제어함을 특징으로 하는 돌기 섬유질형 나노실리카 코어-Zn 기반 배위 고분자 ZIF-8 쉘을 포함하는 나노입자 합성방법.
A methanol solution of the projection-type nano-silica fiber core diameter of 200 ~ 600nm nanoparticles of 2-methyl imidazole, and Zn comprises reacting added 2 + projection fiber-type nano-silica core -Zn-based coordination polymer shell ZIF-8 To synthesize,
The projections 2-a methanol solution of a fiber-type nano-silica core imidazole and Zn + 2 to the reaction carried out two or more times to produce projection-type nano-fiber, which is characterized by controlling the size of nano-particles of silica which is applied the core -Zn Method for synthesizing nanoparticles comprising ZIF-8 shell based coordination polymer.
상기 코어의 외주면에 형성되며, DMF 용액에서 2-메틸이미다졸, Zn2 + 및 2,6-비스[(4-카복시아닐리노)카보닐]피리딘{2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가하여 반응시켜 형성한, 두께 30~1000nm의 Zn 기반 배위 고분자 쉘을 포함하는 나노입자.
Protrusion-type nano-silica / gold nano-dot core with 1 ~ 5nm of gold nano-dots distributed on the surface of projection-type nano-silica having a particle size of 200 ~ 600nm,
It is formed on the outer peripheral surface of the core, and 2-methylimidazole in DMF solution, Zn + 2 and 2,6-bis [(4-carboxy-anilino) carbonyl] pyridine {2,6-bis [(4- carboxyanilino ) carbonyl] pyridine} Nanoparticles comprising a Zn-based coordinating polymer shell having a thickness of 30 to 1000 nm, formed by reacting with a ligand.
상기 코어의 외주면에 형성되며, DMF 용액에서 2-메틸이미다졸, Zn2 + 및 2,6-비스[(4-카복시아닐리노)카보닐]피리딘{2,6-bis[(4-carboxyanilino)carbonyl]pyridine} 리간드를 가하여 반응시켜 형성한, 두께 30~1000nm의 Zn 기반 배위 고분자 쉘을 포함하는 나노입자.
Protrusion fibrous nanosilica / gold nanoparticle core, in which a number of gold nanoparticles of 5-30 nm are distributed on the surface of the protruding fibrous nanosilica having a particle diameter of 200 to 600 nm
It is formed on the outer peripheral surface of the core, and 2-methylimidazole in DMF solution, Zn + 2 and 2,6-bis [(4-carboxy-anilino) carbonyl] pyridine {2,6-bis [(4- carboxyanilino ) carbonyl] pyridine} Nanoparticles comprising a Zn-based coordinating polymer shell having a thickness of 30 to 1000 nm, formed by reacting with a ligand.
상기 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 리간드는 0.01M 내지 0.05M을 가함을 특징으로 하는 나노입자.
The method according to claim 9 or claim 10,
The 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine ligand is a nanoparticle, characterized in that to add 0.01M to 0.05M.
상기 Zn2+ : 2,6-비스[(4-카복시아닐리노)카보닐]피리딘 : 2-메틸이미다졸의 몰비는 2:1:3 ~ 2:2:3임을 특징으로 하는 나노입자.
The method according to claim 9 or claim 10,
The nanoparticles, characterized in that the molar ratio of Zn 2+ : 2,6-bis [(4-carboxycyanilino) carbonyl] pyridine: 2-methylimidazole is 2: 1: 3 to 2: 2: 3.
상기 코어와 배위 고분자 쉘 사이에 공간이 존재함을 특징으로 하는 나노입자.
The method according to claim 9 or claim 10,
Nanoparticles, characterized in that there is a space between the core and the coordination polymer shell.
상기 코어의 외주면에 형성되며, 메탄올 용액에서 2-메틸이미다졸 및 Zn2 +의 반응으로 형성한, 두께 30~1000nm의 Zn 기반 배위 고분자 쉘을 포함하는 나노입자.
Protruding fibrous nanosilica / gold nanoparticle cores with 5-30 nm gold nanoparticles distributed on the surface of the protruding fibrous nanosilica with a particle size of 200 to 600 nm,
Is formed on the outer peripheral surface of the core, the nanoparticles comprising a Zn-based coordination polymer shell of which, 30 ~ 1000nm thickness forming a 2-methanol in solution by the reaction of imidazole and Zn + 2.
상기 Zn2 + : 2-메틸이미다졸의 몰비는 1:2임을 특징으로 하는 나노입자.
The method according to claim 14,
Nanoparticles, characterized in that the molar ratio of the Zn 2 + : 2-methylimidazole is 1: 2.
상기 코어와 쉘 사이에는 공간이 형성됨을 특징으로 하는 나노입자.
The method according to claim 14,
Nanoparticles, characterized in that a space is formed between the core and the shell.
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