KR20230055693A - Method for preparation of platinum nanoparticle-metal oxide composite - Google Patents
Method for preparation of platinum nanoparticle-metal oxide composite Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 71
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002105 nanoparticle Substances 0.000 claims abstract description 45
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 40
- 239000011247 coating layer Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000000231 atomic layer deposition Methods 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 20
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 33
- 239000007789 gas Substances 0.000 description 13
- 150000004706 metal oxides Chemical group 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003993 interaction Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910003446 platinum oxide Inorganic materials 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000351 diffuse reflectance infrared Fourier transform spectroscopy Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- -1 SiO 2 Chemical class 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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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
- B01J37/0225—Coating of metal substrates
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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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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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
- B01J35/002—Catalysts characterised by their physical properties
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- B01J35/30—
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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
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
Description
본 발명은 열적 및 화학적 내구성이 우수한 백금 나노입자-금속 산화물 복합체의 제조 방법, 및 이에 따라 제조된 백금 나노입자-금속 산화물 복합체를 제공하기 위한 것이다. An object of the present invention is to provide a method for preparing a platinum nanoparticle-metal oxide composite having excellent thermal and chemical durability, and a platinum nanoparticle-metal oxide composite prepared according to the method.
백금을 포함한 금속 나노입자 촉매는, 화학적으로 일산화탄소, 포름알데히드, 질소산화물 등 유해 물질을 제거하거나 유용한 고부가가치 화학물질을 제조하는 등 여러 분야에 널리 사용되고 있다. 또한, 상기 외에도 수소 생산 및 수소 활용과 같은 신재생에너지 생산 및 활용을 촉진하는데 중요한 역할을 수행한다.Metal nanoparticle catalysts including platinum are widely used in various fields, such as chemically removing harmful substances such as carbon monoxide, formaldehyde, and nitrogen oxides, or manufacturing useful high value-added chemicals. In addition to the above, it plays an important role in promoting the production and utilization of renewable energy such as hydrogen production and hydrogen utilization.
금속 나노입자는 본질적으로 벌크 물질과 상이한 독특한 성질을 갖고 있으며, 예를 들어 표면 에너지 증가, 융점 강하, 저온 소결성 등의 특성을 나타내 벌크 물질 대비 낮은 내구성을 갖는다. 반면, 대다수의 산업적 촉매 반응은 고온 및 다양한 화학종이 포함된 환경에서 작동하기 때문에, 여기에 금속 나노입자를 촉매로 사용할 경우 낮은 내구성에 기인한 성능 저하가 필연적으로 수반되며, 따라서 금속 나노입자를 산업적으로 사용하기 위해서는 단순한 나노입자 촉매 제조를 넘어 이의 열적 및 화학적 내구성을 개선하는 것이 중요하다.Metal nanoparticles essentially have unique properties that are different from those of bulk materials, and exhibit properties such as increased surface energy, lowered melting point, and low-temperature sinterability, for example, and have lower durability than bulk materials. On the other hand, since most industrial catalytic reactions operate at high temperatures and in an environment containing various chemical species, when metal nanoparticles are used as catalysts, performance degradation due to low durability is inevitably accompanied. It is important to go beyond simple nanoparticle catalyst preparation to improve its thermal and chemical durability.
종래에는 금속 나노입자의 내구성을 확보하기 위해서 나노입자의 표면을 금속 산화물 막에 의해 물리적으로 보호하는 형태의 금속-산화물 코어-쉘 구조체가 많이 제안되었다. 예를 들어, SiO2, TiO2, ZrO2, CeO2 등 다양한 종류의 금속 산화물을 활용한 나노입자 안정화 전략들이 소개되었다. 그러나, 이러한 금속 산화물에 의한 금속 나노입자 안정화 방법은, 유기 작용기 등을 포함한 복잡한 제조 공정이 요구되며 이는 낮은 공정 수율, 높은 공정 비용 및 시간을 수반하므로 경제성이 떨어져 실제 산업에 적용하기에 어렵다는 단점이 있다. Conventionally, in order to secure durability of metal nanoparticles, many metal-oxide core-shell structures in the form of physically protecting the surface of nanoparticles with a metal oxide film have been proposed. For example, nanoparticle stabilization strategies using various types of metal oxides such as SiO 2 , TiO 2 , ZrO 2 , and CeO 2 have been introduced. However, this method of stabilizing metal nanoparticles using metal oxides requires a complicated manufacturing process including organic functional groups, which is accompanied by low process yield, high process cost and time, so it is difficult to apply to the actual industry due to low economic feasibility. there is.
이에 본 발명은, 열적 및 화학적 내구성이 우수한 백금 나노입자-금속 산화물 복합체의 제조 방법을 제공하고자 한다. Accordingly, an object of the present invention is to provide a method for preparing a platinum nanoparticle-metal oxide composite having excellent thermal and chemical durability.
또한, 본 발명은 상기의 제조 방법으로 제조된 백금 나노입자-금속 산화물 복합체를 제공하고자 한다. In addition, the present invention is to provide a platinum nanoparticle-metal oxide composite prepared by the above preparation method.
또한, 본 발명은 상기 백금 나노입자-금속 산화물 복합체를 이용한 촉매를 제공하고자 한다. In addition, the present invention is to provide a catalyst using the platinum nanoparticle-metal oxide complex.
상기 과제를 해결하기 위하여, 본 발명은 이하의 단계를 포함하는 백금 나노입자-금속 산화물 복합체의 제조 방법을 제공한다:In order to solve the above problems, the present invention provides a method for preparing a platinum nanoparticle-metal oxide composite comprising the following steps:
백금 나노입자 표면에, 원자층 증착법으로 망간 산화물 또는 철 산화물 코팅층을 형성하는 단계(단계 1); 및Forming a manganese oxide or iron oxide coating layer on the surface of the platinum nanoparticles by atomic layer deposition (step 1); and
상기 코팅층이 형성된 백금 나노입자를 산화 분위기 하에 열처리하는 단계(단계 2).Heat-treating the platinum nanoparticles on which the coating layer is formed in an oxidizing atmosphere (step 2).
본 발명은 백금 나노입자의 열적 및 화학적 내구성을 향상시키기 위하여, 백금 나노입자의 표면에 금속 산화물을 코팅하는 것으로, 이를 위하여 금속 산화물을 원자층 증착법으로 백금 나노입자 표면에 코팅한 후 산화 분위기에서 열처리하는 것을 특징으로 한다. The present invention is to coat the surface of platinum nanoparticles with a metal oxide in order to improve the thermal and chemical durability of platinum nanoparticles. It is characterized by doing.
원자층 증착법을 사용하기 때문에, 일차로 백금 나노입자의 표면에 금속 산화물 코팅층을 옴스트롱 수준의 두께로 형성할 수 있고, 이어 산화 분위기에서 열처리하여 자발적 에피택시얼(epitaxial) 금속 산화물 코팅층을 형성할 수 있다.Since the atomic layer deposition method is used, a metal oxide coating layer can be formed on the surface of platinum nanoparticles with a thickness of angstroms first, followed by heat treatment in an oxidizing atmosphere to form a spontaneous epitaxial metal oxide coating layer. can
이를 통하여, 백금 나노입자의 표면에 매우 얇은 금속 산화물 코팅층을 형성할 수 있고, 이러한 금속 산화물 코팅층은 백금 나노입자의 표면이 외부 환경에 노출되는 것을 방지하는 동시에 백금 나노입자가 반응에 참여할 수 있는 채널을 제공하는 양면성을 가지게 된다. 그 결과, 본 발명에 따른 백금 나노입자-금속 산화물 복합체는 내구성 측면에서 우수한 열적 및 화학적 안정성을 나타내고, 동시에 촉매 반응성 측면에서 금속 산화물로 코팅되지 않은 백금 나노입자 대비 향상된 반응 특성을 나타낼 수 있다. 이러한 향상된 반응 특성은 우수한 촉매의 내구성으로부터 기인하거나, 백금 나노입자와 금속 산화물 코팅층과의 상호작용(metal-support interaction, MSI)에 기인하거나, 또는 상기 두 가지 효과가 동시에 작용한 것에 기인한다. Through this, it is possible to form a very thin metal oxide coating layer on the surface of the platinum nanoparticles, and this metal oxide coating layer prevents the surface of the platinum nanoparticles from being exposed to the external environment and simultaneously serves as a channel for the platinum nanoparticles to participate in the reaction. It has a duality that provides As a result, the platinum nanoparticle-metal oxide composite according to the present invention may exhibit excellent thermal and chemical stability in terms of durability and, at the same time, improved reaction characteristics compared to platinum nanoparticles not coated with a metal oxide in terms of catalytic reactivity. These improved reaction characteristics are attributed to the excellent durability of the catalyst, the interaction between the platinum nanoparticles and the metal oxide coating layer (metal-support interaction (MSI)), or the simultaneous action of the above two effects.
이하 각 단계 별로 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail for each step.
(단계 1)(Step 1)
본 발명의 단계 1은, 백금 나노입자 표면에, 원자층 증착법으로 망간 산화물 또는 철 산화물 코팅층을 형성하는 단계이다. Step 1 of the present invention is a step of forming a manganese oxide or iron oxide coating layer on the surface of the platinum nanoparticles by an atomic layer deposition method.
바람직하게는, 상기 백금 나노입자는 직경이 1 nm 내지 20 nm이다. 또한, 상기 백금 나노입자는 지지체 상에 담지된 형태일 수 있으며, 이 경우 지지체 상에 백금 나노입자의 표면이 일부 드러나며, 드러난 표면에서 코팅층이 형성된다. Preferably, the platinum nanoparticles have a diameter of 1 nm to 20 nm. In addition, the platinum nanoparticles may be supported on a support, in which case a surface of the platinum nanoparticles is partially exposed on the support, and a coating layer is formed on the exposed surface.
상기 단계 1은 원자층 증착법을 이용하는 것으로, 이를 통하여 망간 산화물 또는 철 산화물을 백금 나노입자의 표면에 옴스트롱 수준의 두께로 형성할 수 있다. Step 1 uses an atomic layer deposition method, through which manganese oxide or iron oxide can be formed to a thickness of the angstrom level on the surface of the platinum nanoparticles.
구체적으로, 상기 원자층 증착법은 백금 나노입자 표면에 망간 산화물 또는 철 산화물, 퍼징 가스, 산화성 가스, 및 퍼징 가스를 순차적으로 노출시키는 것을 한 주기(cycle)로 하여 반복하여 수행할 수 있으며, 상기 망간 산화물 또는 철 산화물의 농도, 상기 반응 가스의 노출 시간, 또는 주기 수행 회수 등을 조절하여, 상기 망간 산화물 또는 철 산화물 코팅층의 두께를 형성할 수 있다. Specifically, the atomic layer deposition method may be repeatedly performed in one cycle by sequentially exposing manganese oxide or iron oxide, a purging gas, an oxidizing gas, and a purging gas on the surface of the platinum nanoparticles. The thickness of the manganese oxide or iron oxide coating layer may be formed by adjusting the concentration of the oxide or iron oxide, the exposure time of the reaction gas, or the number of cycles performed.
한편, 망간 산화물 또는 철 산화물 코팅층을 형성하기 위하여 각각의 전구체를 사용할 수 있다. 예를 들어, 망간의 경우 Mn(TMHD)3((tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III))를, 철의 경우 Ferrocene(Fe(Cp)2)를 사용할 수 있으며, 다만 이에 한정되지 않는다. Meanwhile, each precursor may be used to form a manganese oxide or iron oxide coating layer. For example, Mn(TMHD) 3 ((tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)) for manganese and Ferrocene (Fe(Cp) 2 ) for iron. can be used, but is not limited thereto.
바람직하게는, 상기 망간 산화물 또는 철 산화물 코팅층의 두께가 0.3 nm 내지 1.0 nm가 되도록 상기 단계 1을 수행한다. 상기 코팅층의 두께가 1.0 nm 초과이면 코팅층의 두께가 너무 두껍기 때문에, 최종적으로 제조된 백금 나노입자-금속 복합체에서 백금 나노입자가 반응에 참여할 수 있는 채널을 제공하기 어렵다. 반대로, 상기 코팅층의 두께가 0.3 nm 미만이면 코팅층의 두께가 너무 얇기 때문에, 최종적으로 제조된 백금 나노입자-금속 복합체에서 백금 나노입자의 열적 및 화학적 내구성을 향상시키기 어렵다.Preferably, step 1 is performed so that the thickness of the manganese oxide or iron oxide coating layer is 0.3 nm to 1.0 nm. If the thickness of the coating layer exceeds 1.0 nm, since the thickness of the coating layer is too thick, it is difficult to provide a channel through which the platinum nanoparticles can participate in the reaction in the finally prepared platinum nanoparticle-metal composite. Conversely, if the thickness of the coating layer is less than 0.3 nm, it is difficult to improve the thermal and chemical durability of the platinum nanoparticles in the finally prepared platinum nanoparticle-metal composite because the thickness of the coating layer is too thin.
한편, 상기 원자층 증착법에 사용되는 퍼징 가스로는 당업계에서 널리 사용되는 것이면 특별히 제한되지 않으며, 예를 들어 아르곤 가스, 질소 가스, 헬륨 가스 등 비활성 기체를 사용할 수 있다. Meanwhile, the purging gas used in the atomic layer deposition method is not particularly limited as long as it is widely used in the art, and for example, an inert gas such as argon gas, nitrogen gas, or helium gas may be used.
한편, 상기 단계 1은 25 내지 300℃에서 수행하는 것이 바람직하다. Meanwhile, step 1 is preferably performed at 25 to 300°C.
(단계 2)(Step 2)
본 발명의 단계 2는, 상기 단계 1에서 제조한 코팅층이 형성된 백금 나노입자를 산화 분위기 하에 열처리하는 단계이다.
상기 단계 1에 의하여, 백금 나노입자의 표면에 옴스트롱 수준의 망간 산화물 또는 철 산화물 코팅층이 형성되어 있어, 산화 분위기에서 열처리하면 자발적 에피택시얼(epitaxial) 금속 산화물 코팅층이 형성된다. 이는 서로 다른 물질간의 격자 정합이므로 이종에피텍시(heteroepitaxy)라고도 하며, 백금과 망간 산화물 또는 백금과 철 산화물 간 격자구조 및 격자상수가 유사한 형태로 재배열 되면서 격자가 정합된 에피텍시얼 구조가 형성된다. 이러한 구조를 통해 금속과 산화물 간의 상호 작용이 극대화되는 효과를 얻을 수 있으며, 따라서 향상된 반응 성능과 안정성이 구현될 수 있다. In step 1, since an angstrom-level manganese oxide or iron oxide coating layer is formed on the surface of the platinum nanoparticle, a spontaneous epitaxial metal oxide coating layer is formed when heat treated in an oxidizing atmosphere. Since this is lattice matching between different materials, it is also called heteroepitaxy. As the lattice structure and lattice constant between platinum and manganese oxide or platinum and iron oxide are rearranged in a similar form, an epitaxial structure in which the lattice is matched is formed. is formed Through this structure, the effect of maximizing the interaction between the metal and the oxide can be obtained, and thus improved reaction performance and stability can be implemented.
상기 열처리 온도는 바람직하게는, 400 내지 900℃이고, 보다 바람직하게는 500 내지 800℃이다. The heat treatment temperature is preferably 400 to 900°C, more preferably 500 to 800°C.
바람직하게는, 상기 산화 분위기는 산소 기체를 포함하는 대기 분위기이다. 이때 산소 기체를 포함하는 대기는 산소를 0.1 % 내지 100 % 포함한다. Preferably, the oxidizing atmosphere is an atmospheric atmosphere containing oxygen gas. At this time, the air containing oxygen gas contains 0.1% to 100% of oxygen.
또한, 상기 단계 2는 30분 내지 2시간 동안 수행한다. In addition,
(백금 나노입자-금속 산화물 복합체)(Platinum nanoparticle-metal oxide complex)
본 발명은 상술한 본 발명에 따른 제조 방법에 의하여 제조된 백금 나노입자-금속 산화물 복합체를 제공한다. The present invention provides a platinum nanoparticle-metal oxide composite prepared by the above-described manufacturing method according to the present invention.
본 발명에 따라 백금 나노입자의 표면에 옴스트롱 수준의 망간 산화물 또는 철 산화물 코팅층을 형성할 수 있으며, 이에 본 발명에 따른 백금 나노입자-금속 산화물 복합체는 백금 나노입자의 표면이 외부 환경에 노출되는 것이 방지되어 열적 및 화학적 내구성이 향상된다. According to the present invention, an angstrom-level manganese oxide or iron oxide coating layer can be formed on the surface of platinum nanoparticles, and thus, the platinum nanoparticle-metal oxide composite according to the present invention is suitable for surface exposure of platinum nanoparticles to the external environment. is prevented, thereby improving thermal and chemical durability.
뿐만 아니라, 상기 망간 산화물 또는 철 산화물 코팅층은 결정질의 코팅층으로서 백금 나노입자의 표면이 외부 환경에 노출되는 것을 방지하는 것과 동시에 금속-산화물 상호작용 (metal-support interaction, MSI)를 통해 백금 나노입자가 반응에 참여할 수 있는 채널을 제공한다. 후술할 실시예와 같이, 본 발명에 따른 백금 나노입자-금속 산화물 복합체에서, 백금이 외부로 노출되지 않음에도 불구하고, 백금에 의한 촉매 성능을 나타내며, 따라서 백금 나노입자의 열적 및 화학적 내구성을 향상시킴과 동시에 백금 나노입자의 화학적 특성을 유지 또는 개선할 수 있다. In addition, the manganese oxide or iron oxide coating layer is a crystalline coating layer that prevents the surface of the platinum nanoparticles from being exposed to the external environment and simultaneously prevents the platinum nanoparticles from being exposed to the external environment through metal-support interaction (MSI). Provide a channel to participate in the reaction. As in the examples to be described later, in the platinum nanoparticle-metal oxide composite according to the present invention, even though platinum is not exposed to the outside, catalytic performance by platinum is exhibited, and thus thermal and chemical durability of the platinum nanoparticles is improved. At the same time, it is possible to maintain or improve the chemical properties of the platinum nanoparticles.
따라서, 본 발명에 따른 백금 나노입자-금속 산화물 복합체는, 백금 나노입자의 화학적 특성을 가지고 있으므로, 백금 나노입자가 사용되는 분야, 예컨대 화학적 촉매로 이용될 수 있다. Therefore, since the platinum nanoparticle-metal oxide composite according to the present invention has chemical properties of platinum nanoparticles, it can be used in a field where platinum nanoparticles are used, such as a chemical catalyst.
상술한 바와 같이, 본 발명은 원자층 수준의 망간 산화물 또는 철 산화물 코팅층을 도입하고, 산화 열처리를 통하여 간단하게 백금 나노입자-금속 산화물 복합체를 제조할 수 있고, 대규모 적용이 용이하므로 제조 방법이 경제적이다. 또한, 상기 망간 산화물 또는 철 산화물 코팅층과 같은 산화물 코팅층이 도입된 백금 나노입자는 열적 및 화학적 안정성이 개선되고, 나아가 백금 나노입자의 화학적 특성을 유지 또는 개선할 수 있다.As described above, the present invention introduces a manganese oxide or iron oxide coating layer at the atomic layer level and can simply prepare a platinum nanoparticle-metal oxide composite through oxidation heat treatment, and the manufacturing method is economical because it is easy to apply on a large scale. am. In addition, the thermal and chemical stability of the platinum nanoparticles to which the oxide coating layer such as the manganese oxide or iron oxide coating layer is introduced can be improved, and furthermore, the chemical properties of the platinum nanoparticles can be maintained or improved.
도 1은, 실시예 1 및 2에서 제조한 MnOx/Pt/Al2O3 (800℃ 열처리) 및 FeOx/Pt/Al2O3 (500℃ 열처리)의 표면을 투과전자현미경(TEM)으로 관찰하여 그 결과를 나타낸 것이다.
도 2는, 실시예 1 및 2에서 제조한 MnOx/Pt/Al2O3 및 FeOx/Pt/Al2O3와, 비교예의 Pt/Al2O3에 대한 DRFITS 분석 결과를 나타낸 것이다.
도 3은, 실험예 3에 따른 열적 내구성 평가 결과를 나타낸 것이다.
도 4는, 실험예 4에 따른 화학적 내구성 평가 결과를 나타낸 것이다.
도 5는, 실험예 5에 따른 촉매 특성을 평가한 결과를 나타낸 것이다. 1 shows the surfaces of MnO x /Pt/Al 2 O 3 (heat treatment at 800 ° C) and FeO x /Pt/Al 2 O 3 (heat treatment at 500 ° C) prepared in Examples 1 and 2 using a transmission electron microscope (TEM) was observed and the results were presented.
2 shows the DRFITS analysis results for MnO x /Pt/Al 2 O 3 and FeO x /Pt/Al 2 O 3 prepared in Examples 1 and 2 and Pt/Al 2 O 3 in Comparative Example.
3 shows thermal durability evaluation results according to Experimental Example 3.
4 shows chemical durability evaluation results according to Experimental Example 4.
5 shows the results of evaluating catalyst characteristics according to Experimental Example 5.
이하, 본 발명의 실시예 및 실험예에 대해 상세히 설명한다. 이들 실시예 및 실험예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예 및 실험예에 한정되는 것은 아니다.Hereinafter, examples and experimental examples of the present invention will be described in detail. These Examples and Experimental Examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited to these Examples and Experimental Examples.
실시예 1: 백금 나노입자-금속 산화물 복합체(MnOExample 1: Platinum nanoparticle-metal oxide composite (MnO xx /Pt/Al/Pt/Al 22 OO 33 )의 제조) manufacture of
백금 및 망간 산화물 담지용 산화알루미늄을 지지체로 사용하기 위하여, 상용 Al2O3 분말을 900℃ 분위기에서 24시간 동안 공기 중에서 열처리하여 안정화시켰다. 백금의 경우 Pt(acac)2를 전구체로 사용하여 ALD 1 cycle 공정 진행 후 대기 환경 하에 500℃에서 10분 동안 열처리하여 준비하였다. 이 후, Mn(TMHD)3((tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III))를 전구체로 사용하여 250℃의 온도에서 ALD 55 cycle 공정을 진행해 Pt/Al2O3 위에 망간 산화물을 증착하였다. 망간 산화물 증착 후, 500℃에서 1시간 또는 800℃에서 1시간 동안 대기 분위기에서 열처리를 진행하여, 두 종류의 백금 나노입자-금속 산화물 복합체(MnOx/Pt/Al2O3)를 제조하였다.In order to use aluminum oxide for supporting platinum and manganese oxide as a support, commercial Al 2 O 3 powder was stabilized by heat treatment in air at 900° C. for 24 hours. In the case of platinum, Pt(acac) 2 was used as a precursor and prepared by heat treatment at 500° C. for 10 minutes in an air environment after performing the ALD 1 cycle process. After that, by using Mn(TMHD) 3 ((tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)manganese(III)) as a precursor, an ALD 55 cycle process was performed at a temperature of 250 °C to obtain Pt Manganese oxide was deposited on /Al 2 O 3. After manganese oxide deposition, heat treatment was performed at 500 ° C for 1 hour or 800 ° C for 1 hour in an air atmosphere, and two types of platinum nanoparticle-metal oxide composites (MnO x /Pt/Al 2 O 3 ) was prepared.
실시예 2: 백금 나노입자-금속 산화물 복합체(FeOExample 2: Platinum nanoparticle-metal oxide composite (FeO xx /Pt/Al/Pt/Al 22 OO 33 )의 제조) manufacture of
백금 및 철 산화물 담지용 산화알루미늄을 지지체로 사용하기 위하여, 상용 Al2O3 분말을 900℃ 분위기에서 24시간 동안 공기 중에서 열처리하여 안정화시켰다. 백금의 경우 Pt(acac)2를 전구체로 사용하여 ALD 1 cycle 공정 진행 후 대기 환경 하에 500℃에서 10분 동안 열처리하여 준비하였다. 이 후, Ferrocene(Fe(Cp)2)를 전구체로 사용하여 250oC의 온도에서 ALD 50 cycle 공정을 진행해 Pt/Al2O3 위에 철 산화물을 증착하였다. 철 산화물 증착 후, 500℃에서 1시간 또는 800℃에서 1시간 동안 대기 분위기에서 열처리를 진행하여, 두 종류의 백금 나노입자-금속 산화물 복합체(FeOx/Pt/Al2O3)를 제조하였다.In order to use aluminum oxide for supporting platinum and iron oxide as a support, commercial Al 2 O 3 powder was stabilized by heat treatment in air at 900° C. for 24 hours. In the case of platinum, Pt(acac) 2 was used as a precursor and prepared by heat treatment at 500° C. for 10 minutes in an air environment after performing the ALD 1 cycle process. Thereafter, iron oxide was deposited on Pt/Al 2 O 3 by performing an ALD 50 cycle process at a temperature of 250 ° C using ferrocene (Fe(Cp) 2 ) as a precursor. After iron oxide deposition, heat treatment was performed at 500 °C for 1 hour or 800 °C for 1 hour in an air atmosphere to prepare two types of platinum nanoparticle-metal oxide composites (FeO x /Pt/Al 2 O 3 ).
비교예: 백금 나노입자(Pt/AlComparative Example: Platinum nanoparticles (Pt/Al 22 OO 33 ))
실시예 1 및 2에서 출발 물질로 사용한 알루미늄 산화물에 담지된 백금 나노입자 촉매(Pt/Al2O3)를 비교예로서 사용하였다. A platinum nanoparticle catalyst (Pt/Al 2 O 3 ) supported on aluminum oxide used as a starting material in Examples 1 and 2 was used as a comparative example.
실험예 1Experimental Example 1
상기 실시예 1 및 2에서 제조한 MnOx/Pt/Al2O3 (800℃ 열처리) 및 FeOx/Pt/Al2O3 (500℃ 열처리)의 표면을 투과전자현미경(TEM)으로 관찰하여 그 결과를 도 1에 나타내었다. The surfaces of MnO x /Pt/Al 2 O 3 (heat treatment at 800 ° C) and FeO x /Pt/Al 2 O 3 (heat treatment at 500 ° C) prepared in Examples 1 and 2 were observed with a transmission electron microscope (TEM). The results are shown in Figure 1.
도 1에 나타난 바와 같이, MnOx/Pt/Al2O3 및 FeOx/Pt/Al2O3의 표면에 결정질의 금속 산화물 원자층이 옴스트롱 수준의 두께로 형성되어 있음을 확인할 수 있었다. As shown in FIG. 1 , it was confirmed that a crystalline metal oxide atomic layer was formed on the surfaces of MnO x /Pt/Al 2 O 3 and FeO x /Pt/Al 2 O 3 to a thickness of an angstrom level.
실험예 2Experimental Example 2
상기 실시예 1 및 2에서 제조한 MnOx/Pt/Al2O3 및 FeOx/Pt/Al2O3와, 비교예의 Pt/Al2O3에 대하여, 확산 반사 적외선 푸리에 변환 분광법(diffuse reflectance infrared Fourier transform spectroscopy, 이하 'DRFITS') 분석을 수행하여 가스 흡착 특성을 분석하였다. For MnO x /Pt/Al 2 O 3 and FeO x /Pt/Al 2 O 3 prepared in Examples 1 and 2 and Pt/Al 2 O 3 in Comparative Example, diffuse reflectance infrared Fourier transform spectroscopy (diffuse reflectance Infrared Fourier transform spectroscopy (DRFITS) analysis was performed to analyze gas adsorption characteristics.
구체적으로, DRFITS는 다음과 같이 진행하였다. 먼저, 10% 산소 및 90% 헬륨으로 구성된 혼합 가스 분위기에서 200℃에서 10분 동안 열처리하여 각 시료를 준비하였다. 이 후 25℃의 온도로 하온 시킨 뒤, 10% 일산화탄소 및 90% 헬륨으로 구성된 혼합 가스에 5분간 노출시킨 뒤 100% 헬륨 가스로 10분간 퍼징을 진행한 후 IR 스펙트럼을 관찰하였다. 이 같은 방법으로 CO의 흡착 특성을 분석하였으며, 그 결과를 도 2에 나타내었다. Specifically, DRFITS proceeded as follows. First, each sample was prepared by heat treatment at 200° C. for 10 minutes in a mixed gas atmosphere composed of 10% oxygen and 90% helium. Thereafter, after heating to a temperature of 25 ° C., exposure to a mixed gas composed of 10% carbon monoxide and 90% helium for 5 minutes, purging with 100% helium gas for 10 minutes, and IR spectrum was observed. The adsorption characteristics of CO were analyzed in this way, and the results are shown in FIG. 2 .
도 2에 나타난 바와 같이, MnOx/Pt/Al2O3의 경우 800℃ 산화열처리 이후 현저히 낮은 CO 가스 흡착 특성을 나타내었고, FeOx/Pt/Al2O3의 경우 500℃ 이상의 온도에서 산화 열처리 이후 CO 가스 흡착이 현저히 줄어들었다. 이는 MnOx, FeOx 결정성 원자층 산화물 막이 형성된 투과전자현미경 관찰 결과를 고려하였을때, 각 온도에서 산화 열처리 이후 백금 나노입자 표면이 외부 환경에 노출되지 않음을 나타낸다.As shown in FIG. 2, in the case of MnO x /Pt/Al 2 O 3 , after oxidation heat treatment at 800° C., CO gas adsorption characteristics were significantly lower, and in the case of FeO x /Pt/Al 2 O 3 , oxidation at a temperature of 500° C. or more was observed. After heat treatment, CO gas adsorption was significantly reduced. This indicates that the surface of the platinum nanoparticles is not exposed to the external environment after the oxidation heat treatment at each temperature, considering the transmission electron microscope observation result in which the MnO x and FeO x crystalline atomic layer oxide films are formed.
실험예 3Experimental Example 3
상기 실시예 1에서 제조한 MnOx/Pt/Al2O3 및 비교예의 Pt/Al2O3에 대하여, 열적 및 화학적 내구성 평가를 수행하였다. Thermal and chemical durability were evaluated for MnO x /Pt/Al 2 O 3 prepared in Example 1 and Pt/Al 2 O 3 in Comparative Example.
먼저, 열적 내구성의 경우, 800℃의 대기 상에 복합체를 1시간 동안 노출시킨 뒤 백금 나노입자의 반경이 증가하는 정도를 평가하였다. 그 결과를 각각 하기 표 1 및 도 3에 나타내었다. First, in the case of thermal durability, the degree of increase in the radius of the platinum nanoparticles was evaluated after exposing the composite to the atmosphere at 800 ° C. for 1 hour. The results are shown in Table 1 and FIG. 3 below, respectively.
상기 표 1에 나타난 바와 같이, 비교예는 초기 입자 반경 대비 460%의 증가 폭을 보였으며, MnOx 코팅이 적용된 실시예 1은 233%의 증가 폭을 보이며 코팅 이후 백금 나노입자의 열적 내구성이 향상됨을 보였다. As shown in Table 1, the comparative example showed an increase of 460% compared to the initial particle radius, and Example 1 to which the MnO x coating was applied showed an increase of 233%, and the thermal durability of the platinum nanoparticles was improved after coating showed
또한, 도 3에서도 눈에 띄는 입자 반경의 차이를 확인할 수 있었다.In addition, it was confirmed that there was a noticeable difference in particle radius in FIG. 3 .
다음으로, 화학적 내구성의 경우, 700℃ 4% 프로판(C3H8) 분위기에서 복합체를 12시간 노출시킨 뒤 형성된 카본 침적(carbon coking) 양을 정량 평가하였다. 그 결과를 하기 표 2 및 도 4에 나타내었다. Next, in the case of chemical durability, the amount of carbon coking formed after exposing the composite in a 700°C 4% propane (C 3 H 8 ) atmosphere for 12 hours was quantitatively evaluated. The results are shown in Table 2 and FIG. 4 below.
상기 표 2에 나타난 바와 같이, 비교예는 1,234 μmol의 카본 침적을 나타내었고, MnOx 코팅을 적용한 실시예 1은 375 μmol의 카본 침적을 보이며 코팅을 통해 약 70%의 카본 침적 저감을 확인할 수 있었다 (70% = {(1,234 - 375)/(1,234)} × 100). As shown in Table 2, the comparative example showed 1,234 μmol of carbon deposition, and Example 1 to which the MnO x coating was applied showed 375 μmol of carbon deposition, and it was confirmed that about 70% of carbon deposition was reduced through the coating. (70% = {(1,234 - 375)/(1,234)} × 100).
또한, 도 4에 나타난 바와 같이, 카본 침적 실험 이후, 석영솜에 검정색의 카본 파우더가 발생되었음을 확인할 수 있고, 대조군과 비교해 코팅층 도입을 통하여 카본 침적을 억제되었음을 확인할 수 있었다. In addition, as shown in FIG. 4, after the carbon deposition experiment, it was confirmed that black carbon powder was generated on the quartz wool, and it was confirmed that the carbon deposition was suppressed through the introduction of the coating layer compared to the control group.
실험예 5Experimental Example 5
상기 실시예 1 및 2에서 제조한 MnOx/Pt/Al2O3 (800℃ 열처리) 및 FeOx/Pt/Al2O3 (800℃ 열처리)와, 비교예의 Pt/Al2O3 (800℃ 열처리)에 대하여, 일산화탄소 제거 반응에 적용하여 촉매 반응성을 확인하였다. MnO x /Pt/Al 2 O 3 (heat treatment at 800 ° C) and FeO x /Pt/Al 2 O 3 (heat treatment at 800 ° C) prepared in Examples 1 and 2, and Pt/Al 2 O 3 (800 ° C heat treatment) ℃ heat treatment), it was applied to the carbon monoxide removal reaction to confirm the catalytic reactivity.
구체적으로, 일산화탄소 제거 반응성은 각 복합체 0.1 g을 촉매로 사용하여 2:1의 비율로 CO:O2 혼합가스(28.6 Torr CO, 14.3 Torr O2)를 주입하여 측정하였다. 캐리어 가스는 헬륨을 사용하였으며 총 유량은 106 mL/min으로 통제하였다. 그 결과를 도 5에 나타내었다. Specifically, the carbon monoxide removal reactivity was measured by injecting a CO:O 2 mixed gas (28.6 Torr CO, 14.3 Torr O 2 ) at a ratio of 2:1 using 0.1 g of each composite as a catalyst. Helium was used as the carrier gas and the total flow rate was controlled at 106 mL/min. The results are shown in FIG. 5 .
도 5는 CO 산화 반응 속도를 나타내는 아레니우스 플롯(plot)을 나타내며, 도 5에 나타난 바와 같이 비교예 촉매와 비교하여 MnOx 코팅층이 도입된 백금 나노입자는 약 20배 높은 촉매 특성을 나타내었고, FeOx 코팅층이 도입된 샘플은 약 100배 높은 촉매 특성을 나타내었다. 5 shows an Arrhenius plot showing the CO oxidation reaction rate. As shown in FIG. 5, the platinum nanoparticles introduced with the MnO x coating layer exhibited about 20 times higher catalytic properties compared to the comparative catalyst. , the sample to which the FeO x coating layer was introduced exhibited about 100 times higher catalytic properties.
이와 같은 높은 반응 특성은 우수한 촉매의 내구성으로부터 기인하거나 백금 나노입자와 산화물 코팅층과 상호작용(metal-support interaction, MSI)에 기인하거나 또는 상기 두 가지 효과가 동시에 작용함으로써 나타나는 것으로 판단된다. It is believed that such high reaction characteristics are due to the excellent durability of the catalyst, the interaction between the platinum nanoparticles and the oxide coating layer (metal-support interaction (MSI)), or the simultaneous action of the above two effects.
Claims (10)
상기 코팅층이 형성된 백금 나노입자를 산화 분위기 하에 열처리하는 단계(단계 2)를 포함하는,
백금 나노입자-금속 산화물 복합체의 제조 방법.
Forming a manganese oxide or iron oxide coating layer on the surface of the platinum nanoparticles by atomic layer deposition (step 1); and
Including the step (step 2) of heat-treating the platinum nanoparticles on which the coating layer is formed under an oxidizing atmosphere,
A method for preparing a platinum nanoparticle-metal oxide composite.
상기 백금 나노입자는 직경이 1 nm 내지 20 nm인,
제조 방법.
According to claim 1,
The platinum nanoparticles have a diameter of 1 nm to 20 nm,
manufacturing method.
상기 망간 산화물 또는 철 산화물 코팅층의 두께가 0.3 nm 내지 1.0 nm인,
제조 방법.
According to claim 1,
The thickness of the manganese oxide or iron oxide coating layer is 0.3 nm to 1.0 nm,
manufacturing method.
상기 단계 1은 25 내지 300℃에서 수행하는,
제조 방법.
According to claim 1,
Step 1 is performed at 25 to 300 ° C.
manufacturing method.
상기 단계 2의 열처리 온도는 400 내지 900℃인,
제조 방법.
According to claim 1,
The heat treatment temperature of step 2 is 400 to 900 ° C,
manufacturing method.
상기 산화 분위기는 산소 기체를 포함하는 대기 분위기인,
제조 방법.
According to claim 1,
The oxidizing atmosphere is an atmospheric atmosphere containing oxygen gas,
manufacturing method.
상기 산소 기체를 포함하는 대기는 산소를 0.1 % 내지 100 % 포함하는,
제조 방법.
According to claim 6,
The atmosphere containing the oxygen gas contains 0.1% to 100% oxygen,
manufacturing method.
상기 단계 2는 30분 내지 2시간 동안 수행하는,
제조 방법.
According to claim 1,
Step 2 is performed for 30 minutes to 2 hours,
manufacturing method.
A platinum nanoparticle-metal oxide composite prepared by the method of any one of claims 1 to 8.
A catalyst comprising the platinum nanoparticle-metal oxide complex of claim 9.
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