KR102361486B1 - Preparation method of carbon-supported core-shell type alloy particles catalyst - Google Patents
Preparation method of carbon-supported core-shell type alloy particles catalyst Download PDFInfo
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- KR102361486B1 KR102361486B1 KR1020200037612A KR20200037612A KR102361486B1 KR 102361486 B1 KR102361486 B1 KR 102361486B1 KR 1020200037612 A KR1020200037612 A KR 1020200037612A KR 20200037612 A KR20200037612 A KR 20200037612A KR 102361486 B1 KR102361486 B1 KR 102361486B1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 title claims abstract description 76
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 65
- 239000000956 alloy Substances 0.000 title claims abstract description 65
- 239000011258 core-shell material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title description 8
- 238000006722 reduction reaction Methods 0.000 claims abstract description 39
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims description 110
- 239000002184 metal Substances 0.000 claims description 110
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 96
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 84
- 229910052697 platinum Inorganic materials 0.000 claims description 36
- 239000010949 copper Substances 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 238000006467 substitution reaction Methods 0.000 claims description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
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- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
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- 230000000694 effects Effects 0.000 abstract description 11
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- 230000000052 comparative effect Effects 0.000 description 18
- 229910000881 Cu alloy Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 5
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- 239000012691 Cu precursor Substances 0.000 description 4
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- 238000012790 confirmation Methods 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
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- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004758 underpotential deposition Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- -1 platinum ions Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- 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
- B01J23/8926—Copper 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
- B01J35/0073—Distribution of the active metal ingredient
- B01J35/008—Distribution of the active metal ingredient egg-shell like
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- 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
- B01J37/0221—Coating of particles
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- H—ELECTRICITY
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
본 발명은 탄소-담지 코어-쉘 합금입자 촉매의 제조방법에 관한 것이다.
본 발명의 제조방법에 의하면, 탄소-담지 코어-쉘 구조 합금입자 촉매를 낮은 생산 단가로 대량으로 생산할 수 있는 장점이 있어, 가격 경쟁력 측면에서 유리한 효과가 있다. 또한, 환원제나 계면활성제 등의 화학물질 사용을 제한하여 친환경적이면서, 열처리 및/또는 산처리 등의 공정이 없어 용이하게 탄소-담지 코어-쉘 구조 합금입자 촉매를 제조할 수 있다.
또한, 본 발명에 따른 탄소-담지 코어-쉘 구조 합금입자 촉매는 우수한 산소환원반응 활성 및 내구성을 나타낸다.The present invention relates to a method for preparing a carbon-supported core-shell alloy particle catalyst.
According to the manufacturing method of the present invention, there is an advantage that the carbon-supported core-shell structured alloy particle catalyst can be mass-produced at a low production cost, which has an advantageous effect in terms of price competitiveness. In addition, it is environmentally friendly by limiting the use of chemicals such as reducing agents or surfactants, and there is no process such as heat treatment and/or acid treatment, so that the carbon-supported core-shell structure alloy particle catalyst can be easily prepared.
In addition, the carbon-supported core-shell structured alloy particle catalyst according to the present invention exhibits excellent oxygen reduction reaction activity and durability.
Description
본 발명은 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법에 관한 것이다.The present invention relates to a method for preparing a carbon-supported core-shell structured alloy particle catalyst.
연료전지는 사용하는 연료 및 전해질의 종류에 따라 고분자 전해질형 연료전지(PEMFC), 용융 탄산염 연료전지(MCFC), 고체 산화물 연료전지(SOFC), 직접 메탄올 연료전지(DMFC) 등 다양한 종류가 있으며, 작동 온도에 따라 고온형 또는 저온형으로 분류된다.There are various types of fuel cells, such as polymer electrolyte fuel cells (PEMFC), molten carbonate fuel cells (MCFC), solid oxide fuel cells (SOFC), and direct methanol fuel cells (DMFC), depending on the type of fuel and electrolyte used. According to the operating temperature, it is classified into a high temperature type or a low temperature type.
고분자 전해질형 연료전지의 양극에서 일어나는 산소환원반응은 음극에 비해 상대적으로 느린 반응속도와 복잡한 반응 메커니즘을 가지므로 연료전지의 성능 향상을 위해 활성이 우수한 백금촉매가 주로 사용된다.Since the oxygen reduction reaction occurring in the anode of a polymer electrolyte fuel cell has a relatively slow reaction rate and complex reaction mechanism compared to the cathode, a platinum catalyst with excellent activity is mainly used to improve the performance of the fuel cell.
그러나, 연료전지의 양극촉매로 사용되는 백금 촉매는 매장량이 제한되어 있어 가격이 고가이며, 활성이 우수하나 내구성이 부족하여 장시간 운전 시 활성이 감소하는 것으로 보고되고 있다. 따라서 백금 촉매의 사용량을 줄이고 내구성을 향상시키기 위해 다른 금속과 합금 형태를 이루게 하거나, 산소환원반응에 유리한 결정면을 노출시키기 위해 백금 입자의 형태를 제어하기도 한다. 또한 백금의 사용량을 줄이고자 반응에 참여하지 않는 입자 내부에는 비귀금속이 존재하고 외부에는 백금이 존재하는 코어-쉘 형태의 입자나 입자 내부가 비어있고 껍질에 백금이 존재하는 중공형 입자를 합성하여 연료전지용 촉매로 사용하기도 한다.However, platinum catalysts used as anode catalysts for fuel cells are expensive due to limited reserves, and have excellent activity but lack durability. Therefore, to reduce the amount of platinum catalyst used and to form an alloy with other metals to improve durability, or to control the shape of platinum particles to expose a crystal plane favorable to oxygen reduction reaction. In addition, in order to reduce the amount of platinum used, non-precious metals exist inside the particles that do not participate in the reaction and platinum exists outside, or by synthesizing hollow particles with an empty inside and platinum in the shell. It is also used as a catalyst for fuel cells.
이러한 구조를 제조하기 위해 종래 갈바닉 치환반응을 사용하기도 하였으나, 다음과 같은 한계가 있었다. 즉, 기존의 갈바닉 치환 반응에서의 조건은 첫째, 갈바닉 치환 반응을 유도하기 위해 입자 형틀을 이루게 되는 금속 전구체, 환원제, 계면활성제, 타깃이 되는 금속전구체가 순차적으로 반응기에 들어가게 된다. 이때 입자 형틀이 되는 금속 전구체는 환원제에 의해 환원이 되어 순차적으로 들어오는 금속 전구체와 갈바닉 치환 반응에 의해 이온으로 산화가 되고 타깃이 되는 금속은 환원이 된다. 이와 같은 경우, 고온의 반응 조건이나 고가의 계면활성제를 사용하여 촉매를 제조한 후, 추가 열처리 및/또는 산처리 과정이 필요하다. 이에 따라, 많은 비용과 복잡한 제조과정이 요구되어 대량생산에 부적합하고, 환경에 유해한 단점이 있다.Although a conventional galvanic substitution reaction was used to prepare such a structure, there were the following limitations. That is, the conditions in the existing galvanic substitution reaction are first, the metal precursor, the reducing agent, the surfactant, and the target metal precursor, which form a particle shape to induce the galvanic substitution reaction, are sequentially introduced into the reactor. At this time, the metal precursor serving as the particle frame is reduced by a reducing agent, oxidized into ions by a galvanic substitution reaction with the sequentially incoming metal precursor, and the target metal is reduced. In this case, after the catalyst is prepared using a high-temperature reaction condition or an expensive surfactant, additional heat treatment and/or acid treatment is required. Accordingly, a large amount of cost and a complicated manufacturing process are required, making it unsuitable for mass production and harmful to the environment.
둘째, 타깃이 되는 금속의 크기나 형상을 제어하기 위해서는 계면활성제, 안정제 등이 반응 시 첨가되어야 한다. 이러한 시약은 반응 종료 후에도 완전한 제거가 어려우며 촉매의 활성점을 점유해 촉매 성능 저하의 원인이 된다.Second, in order to control the size or shape of the target metal, a surfactant, a stabilizer, etc. must be added during the reaction. These reagents are difficult to completely remove even after completion of the reaction, and they occupy the active site of the catalyst, causing deterioration of catalyst performance.
셋째, 기존의 갈바닉 치환 반응방법으로 이성분계 이상의 다성분계 합금 나노입자를 합성하기 위해서는 앞선 갈바닉 치환반응에 UPD (underpotential deposition) 방법을 이용해 구리를 금속위에 증착시킨 후, 다시 타깃이 되는 금속전구체와 갈바닉 치환 반응을 거쳐야하며, 이와 같은 방법은 제조 방법이 까다로우며 대량생산이 어렵다는 단점이 있다.Third, in order to synthesize multi-component alloy nanoparticles with two or more components using the existing galvanic substitution reaction method, copper is deposited on the metal using the UPD (underpotential deposition) method in the previous galvanic substitution reaction, and then the target metal precursor and galvanic It has to undergo a substitution reaction, and this method has disadvantages in that the manufacturing method is difficult and mass production is difficult.
이에 따라, 기존의 방법들이 가지고 있던 환경적 문제, 비용적 문제, 과정의 복잡성 등을 해결할 수 있는 탄소-담지 코어-쉘 구조 합금입자 촉매를 제조하는 방법이 요구되고 있다.Accordingly, there is a need for a method for preparing a carbon-supported core-shell structured alloy particle catalyst capable of solving the environmental problems, cost problems, and process complexity of the existing methods.
본 발명의 목적은 기존의 방법에 비해 간단하고, 친환경적이며, 저비용으로 산소환원반응 활성 및 내구성이 우수한 탄소-담지 코어-쉘 구조 합금입자 촉매를 제조하는 방법을 제공하는 것이다. It is an object of the present invention to provide a method for preparing a carbon-supported core-shell structured alloy particle catalyst that is simple, environmentally friendly, and has excellent oxygen reduction activity and durability at low cost compared to conventional methods.
상기한 목적을 달성하기 위하여 본 발명은 (a) 제1금속으로 이루어진 코어 나노입자가 담지된 탄소계 담지체를 증류수에 분산시켜 환원반응용 현탁액을 제조하는 단계; (b) 상기 환원반응용 현탁액에 제2금속 전구체를 첨가한 후 환원반응을 수행함으로써, 상기 담지체에 담지된 상기 제1금속 코어 나노입자; 및 상기 코어 나노입자의 표면에 형성된 제2금속 쉘층;으로 구성된 코어-쉘 구조 합금입자를 포함하는 환원반응 결과액을 수득하는 단계; 및 (c) 상기 환원반응 결과액에 제3금속의 전구체를 첨가한 후 갈바닉 치환반응을 수행함으로써, 상기 제2금속의 일부 또는 전부가 제3금속으로 치환된 코어-쉘 구조의 합금입자를 제조하는 단계;를 포함하는 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법을 제공한다. In order to achieve the above object, the present invention comprises the steps of (a) dispersing a carbon-based support on which core nanoparticles made of a first metal are supported in distilled water to prepare a suspension for a reduction reaction; (b) the first metal core nanoparticles supported on the support by adding a second metal precursor to the suspension for the reduction reaction and then performing a reduction reaction; and a second metal shell layer formed on the surface of the core nanoparticles; a core-shell structured alloy particle comprising: obtaining a resultant solution containing the alloy particles; and (c) adding a precursor of a third metal to the resultant solution of the reduction reaction and then performing a galvanic substitution reaction to prepare alloy particles having a core-shell structure in which part or all of the second metal is substituted with a third metal It provides a method for producing a carbon-supported core-shell structure alloy particle catalyst comprising;
또한, 본 발명은 (A) 탄소계 담지체; (B) 상기 탄소계 담지체에 담지된 복수의 제1금속 나노입자 코어; 및 (C) 상기 복수의 제1금속 나노입자 코어의 표면에 형성된 제2금속 쉘층;을 포함하는 탄소-담지 코어-쉘 구조 합금입자 촉매로서, 상기 쉘층을 형성하는 제2금속의 일부 또는 전부가 제3금속으로 치환되고, 상기 제1금속과 제2금속은 서로 상이하며; 상기 제2금속은 상기 제1금속에 비해 상대적으로 환원력이 높고; 상기 제1금속과 상기 제2금속은 각각 팔라듐(Pd), 니켈(Ni), 코발트(Co), 구리(Cu), 철(Fe), 바나듐(V), 크롬(Cr), 망간(Mn) 및 아연(Zn)으로 이루어진 군에서 선택되며; 상기 제3금속은 백금(Pt)인 것을 특징으로 하는 탄소-담지 코어-쉘 구조 합금입자 촉매를 제공한다.In addition, the present invention is (A) a carbon-based support; (B) a plurality of first metal nanoparticle cores supported on the carbon-based support; and (C) a second metal shell layer formed on the surface of the plurality of first metal nanoparticle cores; a carbon-supported core-shell structure alloy particle catalyst comprising a part or all of the second metal forming the shell layer substituted with a third metal, wherein the first metal and the second metal are different from each other; The second metal has a relatively high reducing power compared to the first metal; The first metal and the second metal are palladium (Pd), nickel (Ni), cobalt (Co), copper (Cu), iron (Fe), vanadium (V), chromium (Cr), and manganese (Mn), respectively. and zinc (Zn); The third metal provides a carbon-supported core-shell structure alloy particle catalyst, characterized in that platinum (Pt).
또한, 본 발명은 상기 방법에 따라 제조된 탄소-담지 코어-쉘 구조 합금입자 촉매를 제공한다.In addition, the present invention provides a carbon-supported core-shell structured alloy particle catalyst prepared according to the above method.
본 발명의 제조방법에 의하면, 탄소-담지 코어-쉘 구조 합금입자 촉매를 낮은 생산 단가로 대량으로 생산할 수 있는 장점이 있어, 가격 경쟁력 측면에서 유리한 효과가 있다. 또한, 환원제나 계면활성제 등의 화학물질 사용을 제한하여 친환경적이면서, 열처리 및/또는 산처리 등의 공정이 없어 용이하게 탄소-담지 코어-쉘 구조 합금입자 촉매를 제조할 수 있다.According to the manufacturing method of the present invention, there is an advantage that the carbon-supported core-shell structured alloy particle catalyst can be mass-produced at a low production cost, which has an advantageous effect in terms of price competitiveness. In addition, it is environmentally friendly by limiting the use of chemicals such as reducing agents or surfactants, and there is no process such as heat treatment and/or acid treatment, so that the carbon-supported core-shell structure alloy particle catalyst can be easily prepared.
또한, 본 발명에 따른 탄소-담지 코어-쉘 구조 합금입자 촉매는 우수한 산소환원반응 활성 및 내구성을 나타낸다.In addition, the carbon-supported core-shell structured alloy particle catalyst according to the present invention exhibits excellent oxygen reduction reaction activity and durability.
도 1은 본 발명에 따라 수용액 내 갈바닉 치환 반응을 이용하여 탄소-담지 코어-쉘 구조 합금입자 촉매를 합성하는 방법을 설명하는 도식이다.
도 2는 본 발명의 실시예 1 내지 4에 따른 탄소-담지 코어-쉘 구조 합금입자 촉매에 있어서, 갈바닉 치환 반응에 의해 백금이 치환되기 전의 팔라듐-구리 합금 입자의 표면 상태를 순환전류법을 이용하여 전기화학적으로 확인한 결과이다.
도 3a는 본 발명의 비교예(상용 Pt/C)에 따른 촉매의 투과전자현미경(TEM) 분석 결과 이미지이다.
도 3b는 본 발명의 실시예 1(Pd/C@Cu@Pt)로부터 제조된 촉매의 투과전자현미경(TEM) 분석 결과 이미지 및 내부에 삽입된 EDS(EDS; Energy dispersive spectroscopy) line scan 이미지이다.
도 4는 본 발명의 실시예 1(Pd/C@Cu@Pt) 및 비교예(상용 Pt/C)에 따른 각각의 촉매의 X선 회절 분석 결과를 나타낸 그래프이다.
도 5는 본 발명의 실시예 1(Pd/C@Cu@Pt) 및 비교예(상용 Pt/C)에 따른 촉매의 선형주사전위법을 통한 가속화된 내구성 실험 전후의 산소환원반응 성능을 비교하기 위한 한그래프이다.1 is a schematic diagram illustrating a method of synthesizing a carbon-supported core-shell structured alloy particle catalyst using a galvanic substitution reaction in an aqueous solution according to the present invention.
2 is in the carbon-supported core-shell structured alloy particle catalyst according to Examples 1 to 4 of the present invention, palladium before platinum is substituted by a galvanic substitution reaction using the cyclic current method. This is the result of electrochemical confirmation.
3A is a transmission electron microscope (TEM) analysis result image of a catalyst according to a comparative example (commercial Pt/C) of the present invention.
3b is a transmission electron microscope (TEM) analysis result image of the catalyst prepared from Example 1 (Pd/C@Cu@Pt) of the present invention and an EDS (energy dispersive spectroscopy) line scan image inserted therein.
4 is a graph showing the results of X-ray diffraction analysis of each catalyst according to Example 1 (Pd/C@Cu@Pt) and Comparative Example (commercial Pt/C) of the present invention.
5 is a comparison of the oxygen reduction reaction performance before and after the accelerated durability test through the linear scanning potential method of the catalyst according to Example 1 (Pd/C@Cu@Pt) and Comparative Example (commercial Pt/C) of the present invention. This is a graph for
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 일 측면은 (a) 제1금속으로 이루어진 코어 나노입자가 담지된 탄소계 담지체를 증류수에 분산시켜 환원반응용 현탁액을 제조하는 단계; (b) 상기 환원반응용 현탁액에 제2금속 전구체를 첨가한 후 환원반응을 수행함으로써, 상기 담지체에 담지된 상기 제1금속 코어 나노입자; 및 상기 코어 나노입자의 표면에 형성된 제2금속 쉘층;으로 구성된 코어-쉘 구조 합금입자를 포함하는 환원반응 결과액을 수득하는 단계; 및 (c) 상기 환원반응 결과액에 제3금속의 전구체를 첨가한 후 갈바닉 치환반응을 수행함으로써, 상기 제2금속의 일부 또는 전부가 제3금속으로 치환된 코어-쉘 구조의 합금입자를 제조하는 단계;를 포함하는 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법에 관한 것이다. One aspect of the present invention comprises the steps of: (a) dispersing a carbon-based support on which core nanoparticles made of a first metal are supported in distilled water to prepare a suspension for a reduction reaction; (b) the first metal core nanoparticles supported on the support by adding a second metal precursor to the suspension for the reduction reaction and then performing a reduction reaction; and a second metal shell layer formed on the surface of the core nanoparticles; a core-shell structured alloy particle comprising: obtaining a resultant solution containing the alloy particles; and (c) adding a precursor of a third metal to the resultant solution of the reduction reaction and then performing a galvanic substitution reaction to prepare alloy particles having a core-shell structure in which part or all of the second metal is substituted with a third metal It relates to a method for producing a carbon-supported core-shell structure alloy particle catalyst comprising a;
일 구현예에 따르면, 상기 제1금속과 제2금속은 서로 상이하고; 상기 제2금속은 상기 제1금속에 비해 상대적으로 환원력이 높으며; 상기 제1금속과 상기 제2금속은 각각 팔라듐(Pd), 니켈(Ni), 코발트(Co), 구리(Cu), 철(Fe), 바나듐(V), 크롬(Cr), 망간(Mn) 및 아연(Zn)으로 이루어진 군에서 선택될 수 있다. 또한, 상기 제3금속은 이리듐(Ir), 백금(Pt) 및 루테늄(Ru)으로 이루어진 군에서 선택된 1종일 수 있다. 바람직한 구현예에 따르면, 상기 제1금속은 팔라듐이고, 상기 제2금속은 구리이며, 상기 제3금속은 백금일 수 있다.According to one embodiment, the first metal and the second metal are different from each other; The second metal has a relatively high reducing power compared to the first metal; The first metal and the second metal are palladium (Pd), nickel (Ni), cobalt (Co), copper (Cu), iron (Fe), vanadium (V), chromium (Cr), and manganese (Mn), respectively. and zinc (Zn). In addition, the third metal may be one selected from the group consisting of iridium (Ir), platinum (Pt), and ruthenium (Ru). According to a preferred embodiment, the first metal may be palladium, the second metal may be copper, and the third metal may be platinum.
또 다른 구현예에 따르면, 상기 제1금속은 팔라듐(Pd), 루테늄 (Ru), 로듐 (Rh), 은 (Ag), 오스뮴 (Os), 이리듐 (Ir), 백금 (Pt), 및 금 (Au)으로 이루어진 군에서 선택된 1종일 수 있다.According to another embodiment, the first metal is palladium (Pd), ruthenium (Ru), rhodium (Rh), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), and gold ( Au) may be one selected from the group consisting of.
또 다른 구현예에 따르면, 상기 제2금속은 니켈(Ni), 코발트(Co), 구리(Cu), 철(Fe), 바나듐(V), 크롬(Cr), 망간(Mn) 및 아연(Zn)으로 이루어진 군에서 선택된 1종일 수 있다.According to another embodiment, the second metal is nickel (Ni), cobalt (Co), copper (Cu), iron (Fe), vanadium (V), chromium (Cr), manganese (Mn) and zinc (Zn) ) may be one selected from the group consisting of.
또 다른 구현예에 따르면, 상기 탄소계 담지체는 벌칸-X(Vulcan-X), 케젠블랙(Ketjen black), 카본블랙, 카본나노튜브, 카본나노파이버, 그래파이트 카본, 그래핀 및 그래핀 옥사이드로 이루어진 군에서 선택된 1종 이상일 수 있다.According to another embodiment, the carbon-based support is Vulcan-X (Vulcan-X), Ketjen black (Ketjen black), carbon black, carbon nanotube, carbon nanofiber, graphite carbon, graphene and graphene oxide It may be one or more selected from the group consisting of.
또 다른 구현예에 따르면, 상기 제1금속 및 제2금속의 몰비는 1 : 0.1-1, 바람직하게는 1 : 0.2-0.8, 더욱 바람직하게는 1 : 0.4-0.6일 수 있다. 또한, 상기 제1금속 및 제3금속의 몰비는 1 : 0.2-0.8, 바람직하게는 0.3-0.7, 더욱 바람직하게는 1 : 0.4-0.6일 수 있다.According to another embodiment, the molar ratio of the first metal and the second metal may be 1:0.1-1, preferably 1:0.2-0.8, more preferably 1:0.4-0.6. In addition, the molar ratio of the first metal and the third metal may be 1:0.2-0.8, preferably 0.3-0.7, more preferably 1:0.4-0.6.
또 다른 구현예에 따르면, 상기 제2금속 전구체는 Cu(NO3)2, Cu(NO3)2·xH2O, CuCl2로 이루어진 군에서 선택된 1종 이상이고, 상기 x는 0.1-10의 실수일 수 있다. 또한, 상기 제3금속 전구체는 H2PtCl6, H2PtCl6·yH2O, K2PtCl6으로 이루어진 군에서 선택된 1종 이상이고; 상기 y는 0.1-10의 실수일 수 있다.According to another embodiment, the second metal precursor is at least one selected from the group consisting of Cu(NO 3 ) 2 , Cu(NO 3 ) 2· xH 2 O, CuCl 2 , wherein x is 0.1-10 It could be a mistake. In addition, the third metal precursor is at least one selected from the group consisting of H 2 PtCl 6 , H 2 PtCl 6· yH 2 O, K 2 PtCl 6 ; The y may be a real number of 0.1-10.
또 다른 구현예에 따르면, 상기 (b) 단계의 환원반응은 수소, 암모니아, 아르곤 및 질소로 이루어진 군에서 선택되는 1종 이상의 기체 분위기에서 수행될 수 있다.According to another embodiment, the reduction reaction of step (b) may be performed in one or more gas atmospheres selected from the group consisting of hydrogen, ammonia, argon and nitrogen.
또 다른 구현예에 따르면, 상기 제조된 탄소-담지 코어-쉘 합금입자 촉매는 진공 오븐에서 40 내지 80 ℃, 바람직하게는 50 내지 70 ℃에서 5 내지 20 시간, 바람직하게는 10 내지 15 시간 동안 건조한 후 사용할 수 있다. According to another embodiment, the prepared carbon-supported core-shell alloy particle catalyst is dried in a vacuum oven at 40 to 80 °C, preferably at 50 to 70 °C for 5 to 20 hours, preferably for 10 to 15 hours. can be used afterwards.
상술한 탄소-담지 코어-쉘 합금입자 촉매의 제조방법은 증류수를 용매로 사용하고, 전체적으로 상온에서 수행되므로, 제조공정이 간단하고 용이하며, 친환경적이고, 경제성이 높은 방법이다. 또한, 촉매의 분리를 위한 공정, 세척 공정, 열처리 공정 및/또는 산처리 공정과 같은 추가적인 처리 없이 바로 이용이 가능하다. The above-described carbon-supported core-shell alloy particle catalyst manufacturing method uses distilled water as a solvent and is performed at room temperature as a whole, so the manufacturing process is simple and easy, eco-friendly, and highly economical. In addition, it can be directly used without additional treatment such as a process for separating the catalyst, a washing process, a heat treatment process, and/or an acid treatment process.
한편, 하기 실시예 또는 비교예 등에 명시적으로 기재하지는 않았지만, 본 발명에 따른 탄소-담지 코어-쉘 합금입자 촉매의 제조방법에 있어서, 제1금속의 종류, 제2금속의 종류, 제3금속의 종류, 제1금속 및 제2금속의 몰비, 제1금속 및 제3금속의 몰비, 환원반응의 조건, 열처리 유무 또는 조건 등을 변화시켜 제조한 각각의 산소환원반응 촉매의 표면을 고배율 TEM을 이용하여 10,000 사이클 진행 전후로 관찰하였다.On the other hand, although not explicitly described in the following examples or comparative examples, in the method for producing a carbon-supported core-shell alloy particle catalyst according to the present invention, the type of the first metal, the type of the second metal, and the third metal The surface of each oxygen reduction reaction catalyst prepared by changing the type of metal, the molar ratio of the first and second metals, the molar ratio of the first and third metals, the conditions of the reduction reaction, the presence or absence of heat treatment, etc. It was observed before and after the progress of 10,000 cycles.
그 결과, 다른 조건 및 다른 수치 범위에서와는 달리 아래 조건이 모두 만족하였을 때에는 촉매 내에 코어-쉘 구조 합금입자가 뭉침 없이 고르게, 균일한 두께로 담지되어 있는 것을 확인할 수 있었다. 또한, 상기 촉매를 이용하여 하기 실험예와 같은 방법으로 10,000 회의 가속화된 내구성 실험을 진행한 후에도 탄소 담지체에 담지된 코어-쉘 구조 합금입자의 유실이 전혀 관찰되지 않아, 내구성이 매우 우수한 것을 확인하였다. As a result, it was confirmed that, unlike other conditions and other numerical ranges, when all of the following conditions were satisfied, the core-shell structured alloy particles were supported in the catalyst with a uniform and uniform thickness without agglomeration. In addition, no loss of the core-shell structure alloy particles supported on the carbon carrier was observed even after 10,000 accelerated durability tests were performed in the same manner as in the following experimental example using the catalyst, confirming that the durability was very good did
① 상기 제1금속은 팔라듐, ② 상기 제2금속은 구리, ③ 상기 제3금속은 백금, ④ 상기 제1금속 및 제2금속의 몰비는 1 : 0.4-0.6, ⑤ 상기 제1금속 및 제3금속의 몰비는 1 : 0.4-0.6, ⑥ 상기 환원반응은 상온 및 수소 분위기 하에서 수행, 및 ⑦ 상기 코어-쉘 합금입자 평균 직경은 3 내지 8 nm.① the first metal is palladium, ② the second metal is copper, ③ the third metal is platinum, ④ the molar ratio of the first metal and the second metal is 1:0.4-0.6, ⑤ the first metal and the third metal The molar ratio of the metal is 1: 0.4-0.6, ⑥ the reduction reaction is performed at room temperature and a hydrogen atmosphere, and ⑦ the core-shell alloy particle average diameter is 3 to 8 nm.
다만, 상기 조건 중 어느 하나라도 충족되지 않는 경우에는 촉매에 포함된 탄소 담지체 내에 코어-쉘 구조 합금입자가 일부 뭉쳐져서 담지되는 것을 확인할 수 있었다. 또한, 탄소 담지체에 코어-쉘 구조 합금입자가 균일하지 않은 두께로 담지됨을 확인하였으며, 10,000 회의 가속화된 내구성 실험 후에 탄소 담지체에 담지된 코어-쉘 구조 합금입자의 일부 유실이 발생하는 것을 확인하였다. However, when any one of the above conditions was not satisfied, it was confirmed that the core-shell structure alloy particles were partially aggregated and supported in the carbon carrier included in the catalyst. In addition, it was confirmed that the core-shell structure alloy particles were supported on the carbon carrier with a non-uniform thickness, and it was confirmed that some loss of the core-shell structure alloy particles supported on the carbon carrier occurred after 10,000 accelerated durability tests. did
본 발명의 다른 측면은 (A) 탄소계 담지체; (B) 상기 탄소계 담지체에 담지된 복수의 제1금속 나노입자 코어; 및 (C) 상기 복수의 제1금속 나노입자 코어의 표면에 형성된 제2금속 쉘층;을 포함하는 탄소-담지 코어-쉘 구조 합금입자 촉매로서, 상기 쉘층을 형성하는 제2금속의 일부 또는 전부가 제3금속으로 치환되고, 상기 제1금속과 제2금속은 서로 상이하며; 상기 제2금속은 상기 제1금속에 비해 상대적으로 환원력이 높고; 상기 제1금속과 상기 제2금속은 각각 팔라듐(Pd), 니켈(Ni), 코발트(Co), 구리(Cu), 철(Fe), 바나듐(V), 크롬(Cr), 망간(Mn) 및 아연(Zn)으로 이루어진 군에서 선택되며; 상기 제3금속은 백금(Pt)인 것을 특징으로 하는 탄소-담지 코어-쉘 구조 합금입자 촉매에 관한 것이다.Another aspect of the present invention is (A) a carbon-based carrier; (B) a plurality of first metal nanoparticle cores supported on the carbon-based support; and (C) a second metal shell layer formed on the surface of the plurality of first metal nanoparticle cores; a carbon-supported core-shell structure alloy particle catalyst comprising a part or all of the second metal forming the shell layer substituted with a third metal, wherein the first metal and the second metal are different from each other; The second metal has a relatively high reducing power compared to the first metal; The first metal and the second metal are palladium (Pd), nickel (Ni), cobalt (Co), copper (Cu), iron (Fe), vanadium (V), chromium (Cr), and manganese (Mn), respectively. and zinc (Zn); The third metal relates to a carbon-supported core-shell structure alloy particle catalyst, characterized in that platinum (Pt).
일 구현예에 따르면, 상기 코어-쉘 합금입자의 평균 직경은 3 내지 8 nm일 수 있다.According to one embodiment, the average diameter of the core-shell alloy particles may be 3 to 8 nm.
다른 구현예에 따르면, 상기 촉매는 연료전지용 촉매(PEMFC(고분자전해질막연료전지), PAFC(인산형연료전지), AEMFC(알칼라인연료전지)), 수전해용 촉매(산소환원반응용 촉매, 수소발생반응용 촉매), CO2 환원 촉매, 인공공합성촉매, 전기화학 합성촉매를 포함하는 전기화학 촉매일 수 있으며, 바람직하게는 산소환원반응용 촉매일 수 있다.According to another embodiment, the catalyst is a catalyst for a fuel cell (PEMFC (polymer electrolyte membrane fuel cell), PAFC (phosphoric acid fuel cell), AEMFC (alkaline fuel cell)), a catalyst for water electrolysis (catalyst for oxygen reduction reaction, hydrogen generation) reaction catalyst), a CO2 reduction catalyst, an artificial co-synthesis catalyst, an electrochemical catalyst including an electrochemical synthesis catalyst, and preferably a catalyst for oxygen reduction reaction.
본 발명의 또 다른 측면은 본 발명의 방법에 의해 제조된 탄소-담지 코어-쉘 구조 합금입자 촉매에 관한 것이다.Another aspect of the present invention relates to a carbon-supported core-shell structured alloy particle catalyst prepared by the method of the present invention.
또한, 본 발명은 상기 탄소-담지 코어-쉘 구조 합금입자 촉매를 포함하는 전극; 및 전해질막을 포함하는 연료전지를 제공한다.In addition, the present invention is an electrode comprising the carbon-supported core-shell structure alloy particle catalyst; and an electrolyte membrane.
상기 연료전지는 본 발명의 탄소-담지 코어-쉘 구조 합금입자 촉매를 채용하여 장기 운전 또는 고온 작동을 하더라도 전극 촉매의 활성이 양호하게 유지된다.The fuel cell employs the carbon-supported core-shell structured alloy particle catalyst of the present invention to maintain good electrode catalyst activity even during long-term operation or high-temperature operation.
상기 연료전지는 노트북, 휴대용 전자기기, 자동차, 버스 등을 포함하는 이동용 및 가정용 연료전지일 수 있다.The fuel cell may be a fuel cell for mobile and home use including notebook computers, portable electronic devices, automobiles, buses, and the like.
이하에서 실시예 등을 통해 본 발명을 더욱 상세히 설명하고자 하며, 다만 이하에 실시예 등에 의해 본 발명의 범위와 내용이 축소되거나 제한되어 해석될 수 없다. 또한, 이하의 실시예를 포함한 본 발명의 개시 내용에 기초한다면, 구체적으로 실험 결과가 제시되지 않은 본 발명을 통상의 기술자가 용이하게 실시할 수 있음은 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허 청구범위에 속하는 것도 당연하다.Hereinafter, the present invention will be described in more detail by way of Examples and the like, but the scope and content of the present invention may not be construed as being reduced or limited by the Examples below. In addition, based on the disclosure of the present invention including the following examples, it is clear that a person skilled in the art can easily practice the present invention for which no specific experimental results are presented, and such variations and modifications are included in the attached patent It goes without saying that it falls within the scope of the claims.
<실시예> <Example>
도 1은 본 발명에 따라 수용액 내 갈바닉 치환 반응을 이용하여 탄소-담지 코어-쉘 구조 합금입자 촉매를 합성하는 방법을 설명하는 도식이다.1 is a schematic diagram illustrating a method of synthesizing a carbon-supported core-shell structured alloy particle catalyst using a galvanic substitution reaction in an aqueous solution according to the present invention.
도 1을 참조하면, 본 발명의 일 실시예에 따른 촉매의 제조방법은 (1) 탄소에 담지된 나노 크기의 금속 코어(제1금속; 팔라듐) 위에 이종금속(제2금속; 구리)의 금속 전구체를 환원시키면서 증착시키는 단계; 및 (2) 갈바닉 치환 반응에 의해 상기 금속 코어(팔라듐)에 증착된 이종금속(구리)와 백금(제3금속)의 전구체를 치환시키는 단계로 구성된다. 이때, 상기 제1금속 및/또는 제2금속은 상기 팔라듐 및/또는 구리 이외에도 제3금속(백금)과 표준환원전위 차이가 나는 원소를 다양하게 선택하는 것이 가능하다.Referring to FIG. 1 , in the method for preparing a catalyst according to an embodiment of the present invention, (1) a metal of a dissimilar metal (second metal; copper) on a nano-sized metal core (first metal; palladium) supported on carbon depositing the precursor while reducing; and (2) substituting a precursor of a dissimilar metal (copper) and platinum (third metal) deposited on the metal core (palladium) by a galvanic substitution reaction. In this case, as the first metal and/or the second metal, it is possible to variously select an element having a standard reduction potential difference from the third metal (platinum) in addition to the palladium and/or copper.
실시예 1. 탄소-담지 코어-쉘 합금입자(Pd/C@CuExample 1. Carbon-supported core-shell alloy particles (Pd/C@Cu) 1/21/2 @Pt) 촉매의 제조@Pt) Preparation of catalyst
(a) 먼저, 상업용 탄소계 담지체에 담지된 팔라듐 촉매(Pd/C)(Premetek Co)를 준비하였다. 그리고, 상기 상업용 탄소계 담지체에 담지된 팔라듐 촉매 50 mg을 100 ml의 증류수에 분산시켜 환원반응용 현탁액을 제조하였다.(a) First, a palladium catalyst (Pd/C) (Premetek Co) supported on a commercial carbon-based support was prepared. Then, 50 mg of the palladium catalyst supported on the commercial carbon-based support was dispersed in 100 ml of distilled water to prepare a suspension for reduction reaction.
(b) 반응기에 상기 환원반응용 현탁액을 넣은 후, 반응기 내의 가스를 50 vol%의 수소 가스로 교체하고, 총 2시간 동안 불어넣어 주었다. 그리고, 상기 환원반응용 현탁액에 구리 전구체, CuCl2(Sigma-Aldrich Co) stock solution(10 ml 증류수 당 1 g) 80 ㎕를 투입하였다. 이때, 몰수 기준으로 팔라듐 대비 구리 함량은 1 : 0.5이었다. 이후, 환원반응을 유도하기 위하여, 상기 반응기에 50 vol%의 수소 가스를 4 시간 동안 불어넣었다.(b) After putting the suspension for the reduction reaction in the reactor, the gas in the reactor was replaced with 50 vol% hydrogen gas, and it was blown for a total of 2 hours. Then, 80 μl of a copper precursor, CuCl 2 (Sigma-Aldrich Co) stock solution (1 g per 10 ml of distilled water) was added to the suspension for the reduction reaction. At this time, based on the number of moles, the copper content compared to palladium was 1:0.5. Then, in order to induce a reduction reaction, 50 vol% of hydrogen gas was blown into the reactor for 4 hours.
(c) 이후, 상기 반응기에 100 vol%의 질소 가스를 1 시간 동안 불어넣어 질소 기체 분위기를 조성하였으며, 3차 증류수에 녹인 백금 전구체, H2PtCl6(KOJIMA Co) 50 ml를 교반 중에 한 방울씩 5 ml/min의 속도로 떨어뜨려 구리와 백금 이온 간의 갈바닉 치환 반응을 유도하였으며, 2 시간 동안 반응이 이루어지도록 하였다. 이때, 몰수 기준으로 팔라듐 대비 백금 함량은 1 : 0.5이었다. (c) After that, 100 vol% nitrogen gas was blown into the reactor for 1 hour to create a nitrogen gas atmosphere, and 50 ml of a platinum precursor, H 2 PtCl 6 (KOJIMA Co) dissolved in tertiary distilled water, was added while stirring one drop. Each was dropped at a rate of 5 ml/min to induce a galvanic substitution reaction between copper and platinum ions, and the reaction was allowed to take place for 2 hours. At this time, based on the number of moles, the platinum content compared to palladium was 1:0.5.
(d) 상기 갈바닉 치환 반응이 완료된 코어-쉘 합금입자를 필터링한 후, 12 시간 이상 진공 건조하여, 탄소-담지 코어-쉘 합금입자 촉매(Pd/C@Cu1/0.5@Pt)를 제조하였다.(d) After filtering the core-shell alloy particles on which the galvanic substitution reaction has been completed, vacuum drying for 12 hours or more to prepare a carbon-supported core-shell alloy particle catalyst (Pd/C@Cu 1/0.5 @Pt) .
실시예 2. 탄소-담지 코어-쉘 합금입자(Pd/C@CuExample 2. Carbon-supported core-shell alloy particles (Pd/C@Cu) 1/11/1 @Pt) 촉매의 제조@Pt) Preparation of catalyst
실시예 1과 동일한 방법으로 실시하되, 구리 전구체 stock solution의 투입량을 조절하여 몰수 기준으로 팔라듐 대비 구리의 양을 1 : 1로 조절하여, 탄소-담지 코어-쉘 합금입자 촉매(Pd/C@Cu1/1@Pt)를 제조하였다. It was carried out in the same manner as in Example 1, except that the amount of copper compared to palladium was adjusted to 1:1 based on the number of moles by adjusting the amount of the copper precursor stock solution, and the carbon-supported core-shell alloy particle catalyst (Pd/C@Cu) 1/1 @Pt) was prepared.
실시예 3. 탄소-담지 코어-쉘 합금입자(Pd/C@CuExample 3. Carbon-supported core-shell alloy particles (Pd/C@Cu) 1/51/5 @Pt) 촉매의 제조@Pt) Preparation of catalyst
실시예 1과 동일한 방법으로 실시하되, 구리 전구체 stock solution의 투입량을 조절하여 몰수 기준으로 팔라듐 대비 구리의 양을 1 : 0.2로 조절하여, 탄소-담지 코어-쉘 합금입자 촉매(Pd/C@Cu1/5@Pt)를 제조하였다. It was carried out in the same manner as in Example 1, except that the amount of copper compared to palladium was adjusted to 1: 0.2 based on the number of moles by adjusting the amount of the copper precursor stock solution, and the carbon-supported core-shell alloy particle catalyst (Pd/C@Cu) 1/5 @Pt) was prepared.
실시예 4. 탄소-담지 코어-쉘 합금입자(Pd/C@CuExample 4. Carbon-supported core-shell alloy particles (Pd/C@Cu) 1/101/10 @Pt) 촉매의 제조@Pt) Preparation of catalyst
실시예 1과 동일한 방법으로 실시하되, 구리 전구체 stock solution의 투입량을 조절하여 몰수 기준으로 팔라듐 대비 구리의 양을 1 : 0.1로 조절하여, 탄소-담지 코어-쉘 합금입자 촉매(Pd/C@Cu1/10@Pt)를 제조하였다. It was carried out in the same manner as in Example 1, except that the amount of copper compared to palladium was adjusted to 1:0.1 based on the number of moles by adjusting the amount of the copper precursor stock solution, and the carbon-supported core-shell alloy particle catalyst (Pd/C@Cu) 1/10 @Pt) was prepared.
비교예. 상업용 백금 촉매의 준비comparative example. Preparation of Commercial Platinum Catalyst
상업용 탄소 담지 백금 촉매(Pt/C)(Johnson Matthey Co, HISPEC 3000)를 준비하였다.A commercial carbon-supported platinum catalyst (Pt/C) (Johnson Matthey Co, HISPEC 3000) was prepared.
실험예 1. 백금이 치환되기 전의 팔라듐-구리 합금입자의 표면 상태 확인Experimental Example 1. Confirmation of surface state of palladium-copper alloy particles before platinum is substituted
실시예의 팔라듐-구리 합금입자에 있어서, 상기 팔라듐에 대한 구리 함량 변화에 따라 합금입자의 표면 상태가 어떻게 달라지는지를 전류순환법(Cyclic Voltammetry, CV)을 이용하여 확인하고자 하였다.In the palladium-copper alloy particles of the embodiment, it was tried to confirm how the surface state of the alloy particles changes according to the change in the copper content for the palladium by using a cyclic voltammetry (CV).
이를 위하여, 실시예 1 내지 4에서 제조된 팔라듐-구리 합금입자 10 mg을 800 ㎕의 IPA 용액 및 60 ㎕의 나피온 용액(5 중량% 용액)의 혼합 용액에 넣고 초음파를 이용하여 분산하여 잉크 형태로 제조하였다. 제조된 촉매 잉크 20 ㎕를 마이크로피펫을 이용하여 유리 카본 회전 디스크 전극(RDE, 0.196 ㎠) 상에 옮겨놓고, 건조시켜 알코올을 증발시켰다. 그리고, 일정전위기를 이용하여 전압에 따른 전류 특성을 측정하였다(0.1 M HClO4 전해질, 아르곤 분위기). To this end, 10 mg of the palladium-copper alloy particles prepared in Examples 1 to 4 were placed in a mixed solution of 800 μl of IPA solution and 60 μl of Nafion solution (5 wt% solution) and dispersed using ultrasound to form an ink. was prepared with 20 μl of the prepared catalyst ink was transferred onto a glass carbon rotating disk electrode (RDE, 0.196 cm 2 ) using a micropipette, dried, and alcohol was evaporated. Then, the current characteristics according to the voltage were measured using a constant potential (0.1 M HClO 4 electrolyte, argon atmosphere).
도 2는 본 발명의 실시예 1 내지 4에 따른 탄소-담지 코어-쉘 구조 합금입자 촉매에 있어서, 갈바닉 치환 반응에 의해 백금이 치환되기 전의 팔라듐-구리 합금입자의 표면 상태를 전류순환법을 이용하여 전기화학적으로 확인한 결과이다.Figure 2 is in the carbon-supported core-shell structure alloy particle catalyst according to Examples 1 to 4 of the present invention, palladium before platinum is substituted by a galvanic substitution reaction - the surface state of the copper alloy particles using the current circulation method This is the result of electrochemical confirmation.
도 2를 살펴보면, 비교적 구리 함량이 적은 실시예 3(Pd/C@Cu1/5) 및 실시예 4(Pd/C@Cu1/10)의 팔라듐-구리 합금입자의 경우 수소 흡/탈착 영역의 피크와 표면 OH 생성/환원 피크의 개형이 단일 팔라듐 표면과 유사한 것을 확인할 수 있다. 또한, 비교적 구리 함량이 높은 실시예 2(Pd/C@Cu1/1)의 팔라듐-구리 합금입자의 경우 표면에서 구리 입자에 대한 전류 특성이 우세해지는 것을 확인할 수 있다. 한편, 최적의 구리 함량을 가진 실시예 1(Pd/C@Cu1/2)의 팔라듐-구리 합금입자의 경우 팔라듐과 구리 사이의 강한 영향으로 새로운 위치의 수소 탈착 피크가 나타나고, OH 생성 피크는 크게 감소하였으며, 전반적으로 전류 특성이 감소하는 것을 확인할 수 있다. 이는 팔라듐 표면의 구리가 단일 원자층을 형성하거나 서브-나노 단위 두께로 쉘층을 형성한 것으로 볼 수 있다. Referring to Figure 2, in the case of the palladium-copper alloy particles of Example 3 (Pd/C@Cu 1/5 ) and Example 4 (Pd/C@Cu 1/10 ) having a relatively low copper content, hydrogen adsorption/desorption region It can be seen that the shape of the peak and the surface OH generation/reduction peak are similar to that of a single palladium surface. In addition, in the case of the palladium-copper alloy particles of Example 2 (Pd/C@Cu 1/1 ) having a relatively high copper content, it can be confirmed that the current characteristics for the copper particles are dominant on the surface. On the other hand, in the case of the palladium-copper alloy particles of Example 1 (Pd/C@Cu 1/2 ) having an optimal copper content, a hydrogen desorption peak at a new position appears due to the strong influence between palladium and copper, and the OH generation peak is It was significantly reduced, and it can be seen that the overall current characteristics are reduced. This can be considered that the copper on the palladium surface forms a single atomic layer or a shell layer with a sub-nano unit thickness.
실험예 2. 투과전자현미경(TEM) 분석Experimental Example 2. Transmission electron microscope (TEM) analysis
투과전자현미경(TEM; Transmission electron microscopy)을 이용하여 상기 실시예 및 비교예에서 얻은 촉매를 분석하였다.The catalysts obtained in Examples and Comparative Examples were analyzed using a transmission electron microscope (TEM).
도 3a는 본 발명의 비교예(상용 Pt/C)에 따른 촉매의 투과전자현미경(TEM) 분석 결과 이미지이다. 상기 도 3a를 살펴보면, 비교예에 따른 상용 백금 촉매 내의 백금 나노입자는 3~6 nm의 크기를 가지고 있으며, 일반적으로 전기화학 촉매에서 사용되는 백금 나노입자 형태를 나타내고 있다.3A is a transmission electron microscope (TEM) analysis result image of a catalyst according to a comparative example (commercial Pt/C) of the present invention. Referring to FIG. 3A , the platinum nanoparticles in the commercial platinum catalyst according to Comparative Example have a size of 3 to 6 nm, and generally show the form of platinum nanoparticles used in electrochemical catalysts.
도 3b는 본 발명의 실시예 1(Pd/C@Cu@Pt)로부터 제조된 촉매의 투과전자현미경(TEM) 분석 결과 이미지 및 내부에 삽입된 EDS(EDS; Energy dispersive spectroscopy) line scan 그래프이다. 상기 도 3b를 살펴보면, 실시예 1에 따른 촉매 내의 코어-쉘 합금 나노입자는 3~8 nm의 크기를 가지고 있는 것을 확인할 수 있다. 또한, 상기 도 3b 내부에 삽입된 EDS line scan 이미지는 촉매 내의 합금입자 내의 금속의 분포를 나타낸 것으로, 약 6 nm 크기를 가지는 입자를 관찰하였을 때에 실시예 1에 따른 촉매 내의 합금입자가 팔라듐과 백금으로 구성된 코어-쉘 구조인 것을 확인할 수 있다. 이는 실시예 1의 촉매 제조 과정에서, 팔라듐 코어 표면의 구리가 백금으로 치환된 것을 의미한다.3b is a transmission electron microscope (TEM) analysis result image of the catalyst prepared from Example 1 (Pd/C@Cu@Pt) of the present invention and an EDS (energy dispersive spectroscopy) line scan graph inserted therein. Referring to FIG. 3B , it can be seen that the core-shell alloy nanoparticles in the catalyst according to Example 1 have a size of 3 to 8 nm. In addition, the EDS line scan image inserted in FIG. 3b shows the distribution of metal in the alloy particles in the catalyst. When particles having a size of about 6 nm were observed, the alloy particles in the catalyst according to Example 1 were palladium and platinum. It can be seen that the core-shell structure is composed of This means that, in the catalyst preparation process of Example 1, copper on the surface of the palladium core was substituted with platinum.
실험예 3. X선 회절 분석Experimental Example 3. X-ray diffraction analysis
X선 회절(XRD; X-ray diffraction)을 이용하여 상기 실시예 1 및 비교예에 따른 탄소-담지 코어-쉘 합금 입자 촉매의 결정성을 분석하였다. 도 4는 본 발명의 실시예 1(Pd/C@Cu@Pt) 및 비교예(상용 Pt/C)에 따른 각각의 촉매의 X선 회절 분석 결과를 나타낸 그래프이다.The crystallinity of the carbon-supported core-shell alloy particle catalyst according to Example 1 and Comparative Example was analyzed using X-ray diffraction (XRD). 4 is a graph showing the results of X-ray diffraction analysis of each catalyst according to Example 1 (Pd/C@Cu@Pt) and Comparative Example (commercial Pt/C) of the present invention.
도 4를 살펴보면, 실시예 1 및 비교예에 따른 탄소-담지 코어-쉘 합금 입자 모두 백금의 기본 결정구조인 면심입방격자(FCC) 구조를 가지고 있는 것을 확인할 수 있었다.Referring to FIG. 4 , it was confirmed that all of the carbon-supported core-shell alloy particles according to Example 1 and Comparative Example had a face-centered cubic (FCC) structure, which is a basic crystal structure of platinum.
한편, 실시예 1에 따른 촉매의 경우 상대적으로 백금보다 더 낮은 각도에서 피크가 나타나는 팔라듐이 존재함에도 불구하고, 상용 백금 촉매(비교예)보다 더 높은 각도에서 피크가 관찰되었다. 이는 실시예 1의 촉매 제조과정에서 백금과 치환되지 않고 남아있는 구리의 존재로 인해 표면 백금층 및/또는 촉매 전반에 압축 변형이 가해졌기 때문인 것으로 판단된다. 이를 통해 실시예에 따른 촉매의 표면 백금층의 전기화학적 활성이 변화된 것을 예측할 수 있다.On the other hand, in the case of the catalyst according to Example 1, a peak was observed at a higher angle than that of a commercially available platinum catalyst (Comparative Example), despite the presence of palladium showing a peak at a relatively lower angle than platinum. This is considered to be because compressive deformation was applied to the entire surface of the platinum layer and/or the catalyst due to the presence of copper remaining unsubstituted with platinum in the catalyst preparation process of Example 1. Through this, it can be predicted that the electrochemical activity of the surface platinum layer of the catalyst according to the embodiment is changed.
실험예 4. 내구성 평가 - 선형주사전위법(Linear sweep voltammetry, LSV)Experimental Example 4. Durability evaluation - Linear sweep voltammetry (LSV)
실시예 1 및 비교예의 촉매에 대해 선형주사전위법을 이용하여 산소환원반응에 대한 전기화학적 활성을 평가하였다. For the catalysts of Example 1 and Comparative Example, the electrochemical activity for the oxygen reduction reaction was evaluated using the linear scanning potential method.
상기 산소환원반응 성능은 상기 실험예 1의 전류순환법 측정과 마찬가지로 촉매를 잉크 형태로 만들어 회전 디스크 전극에 올린 후 일정전위기를 이용하여 분석하였다. 0.1 M HClO4 전해질 용액에 산소 가스를 지속적으로 공급해주어 포화된 상태로 만든 후에 상온에서 산소환원반응 성능을 측정하였고, 그 결과를 도 5에 나타내었다. 상기 산소환원반응 성능은 회전 원판 전극 방법에 따라 평가하였으며, 낮은 전압부터 높은 전압으로 전압을 변화시키면서(10 mV/s 스캔속도) 전류를 관찰하였고, 1600 rpm으로 전극을 회전시키며 분극곡선을 얻었다.The oxygen reduction reaction performance was analyzed by using a constant potential after making a catalyst in the form of ink and placing it on a rotating disk electrode similarly to the measurement of the current circulation method of Experimental Example 1. Oxygen gas was continuously supplied to 0.1 M HClO 4 electrolyte solution to make it saturated, and then the oxygen reduction reaction performance was measured at room temperature, and the results are shown in FIG. 5 . The oxygen reduction reaction performance was evaluated according to the rotating disk electrode method, the current was observed while changing the voltage from a low voltage to a high voltage (10 mV/s scan rate), and a polarization curve was obtained by rotating the electrode at 1600 rpm.
도 5는 본 발명의 실시예 1(Pd/C@Cu@Pt) 및 비교예(상용 Pt/C)에 따른 촉매의 선형주사전위법을 통한 가속화된 내구성 실험 전후의 산소환원반응 성능을 비교하기 위한 그래프이다. 도 5를 살펴보면, 실시예 1의 촉매가 비교예에 비해 우수한 반응성을 가지는 것을 확인할 수 있었다. 5 is a comparison of the oxygen reduction reaction performance before and after the accelerated durability test through the linear scanning potential method of the catalyst according to Example 1 (Pd/C@Cu@Pt) and Comparative Example (commercial Pt/C) of the present invention. This is a graph for Referring to FIG. 5 , it was confirmed that the catalyst of Example 1 had superior reactivity compared to Comparative Example.
또한, 추가적으로 촉매의 내구성을 알아보기 위해 실시예 1 및 비교예에 따른 촉매를 10,000회 가량의 가속화된 내구성 실험(1회당 0.65-1.05-0.65V의 전압순환, 100 mV/s 스캔속도)을 진행하였다. 상기 내구성 실험 후 산소환원반응 전류를 측정한 결과 비교예의 경우 상당히 감소하였지만, 실시예 1의 촉매는 성능이 유지되는 것을 확인할 수 있었다.In addition, in order to additionally examine the durability of the catalyst, accelerated durability experiments (voltage cycle of 0.65-1.05-0.65V per one time, 100 mV/s scan rate) were performed on the catalysts according to Example 1 and Comparative Example for about 10,000 times. did As a result of measuring the oxygen reduction reaction current after the durability test, the comparative example significantly decreased, but it was confirmed that the catalyst of Example 1 maintained its performance.
이러한 결과는 본 발명의 실시예에 따른 촉매가 비교예의 촉매에 비해 현저히 우수한 내구성을 가지는 것을 의미한다. 또한, 실시예에 따른 촉매가 저가의 연료전지용 산소환원반응 촉매의 소재로서 적용 가능함을 보여준다.These results mean that the catalyst according to the embodiment of the present invention has significantly superior durability compared to the catalyst of the comparative example. In addition, it shows that the catalyst according to the embodiment can be applied as a material for a low-cost oxygen reduction catalyst for fuel cells.
비록 본 발명이 상기에 언급된 바람직한 실시예로서 설명되었으나, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 또한, 첨부된 청구범위는 본 발명의 요지에 속하는 이러한 수정이나 변형을 포함한다.Although the present invention has been described as the above-mentioned preferred embodiment, it is possible to make various modifications and variations without departing from the spirit and scope of the invention. It is also intended that the appended claims cover such modifications and variations as fall within the scope of the present invention.
Claims (15)
(b) 상기 환원반응용 현탁액에, 제2금속 전구체 수용액을 첨가한 후 상온에서 환원반응을 수행함으로써, 상기 담지체에 담지된 상기 제1금속 코어 나노입자; 및 상기 코어 나노입자의 표면에 형성된 제2금속 쉘층;으로 구성된 코어-쉘 구조 합금입자를 포함하는 환원반응 결과액을 수득하는 단계; 및
(c) 상기 환원반응 결과액에, 제3금속 전구체 수용액을 첨가한 후 갈바닉 치환반응을 수행함으로써, 상기 제2금속의 일부 또는 전부가 제3금속으로 치환된 코어-쉘 구조의 합금입자를 제조하는 단계;를 포함하고,
상기 제1금속과 제2금속은 서로 상이하며;
상기 제2금속은 상기 제1금속에 비해 상대적으로 환원력이 높고;
상기 제1금속과 상기 제2금속은 각각 팔라듐(Pd), 니켈(Ni), 코발트(Co), 구리(Cu), 철(Fe), 바나듐(V), 크롬(Cr), 망간(Mn) 및 아연(Zn)으로 이루어진 군에서 선택되며;
상기 제3금속은 백금(Pt)이고,
상기 제1금속 및 제2금속의 몰비는 1 : 0.1-1이고,
상기 제1금속 및 제3금속의 몰비는 1 : 0.2-0.8인 것을 특징으로 하는 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법. (a) preparing a suspension for a reduction reaction by dispersing a carbon-based support on which core nanoparticles made of a first metal are supported in distilled water;
(b) the first metal core nanoparticles supported on the support by adding an aqueous solution of a second metal precursor to the suspension for the reduction reaction and then performing a reduction reaction at room temperature; and a second metal shell layer formed on the surface of the core nanoparticles; a core-shell structured alloy particle comprising: obtaining a resultant solution containing the alloy particles; and
(c) by adding a third metal precursor aqueous solution to the reduction reaction resultant solution and then performing a galvanic substitution reaction, to prepare alloy particles having a core-shell structure in which a part or all of the second metal is substituted with a third metal including;
the first metal and the second metal are different from each other;
The second metal has a relatively high reducing power compared to the first metal;
The first metal and the second metal are each of palladium (Pd), nickel (Ni), cobalt (Co), copper (Cu), iron (Fe), vanadium (V), chromium (Cr), and manganese (Mn) and zinc (Zn);
The third metal is platinum (Pt),
The molar ratio of the first metal and the second metal is 1: 0.1-1,
The molar ratio of the first metal and the third metal is 1: 0.2-0.8. Carbon-supported core-shell structure alloy particle catalyst manufacturing method.
상기 탄소계 담지체는 벌칸-X(Vulcan-X), 케젠블랙(Ketjen black), 카본블랙, 카본나노튜브, 카본나노파이버, 그래파이트 카본, 그래핀 및 그래핀 옥사이드로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법. According to claim 1,
The carbon-based carrier is at least one selected from the group consisting of Vulcan-X, Ketjen black, carbon black, carbon nanotubes, carbon nanofibers, graphite carbon, graphene and graphene oxide. Method for producing a carbon-supported core-shell structure alloy particle catalyst, characterized in that.
상기 제1금속은 팔라듐이고, 상기 제2금속은 구리이며, 상기 제3금속은 백금이고;
상기 제2금속 전구체는 Cu(NO3)2, Cu(NO3)2·xH2O 및 CuCl2로 이루어진 군에서 선택된 1종 이상이고; 상기 x는 0.1-10의 실수이며;
상기 제3금속 전구체는 H2PtCl6, H2PtCl6·yH2O 및 K2PtCl6으로 이루어진 군에서 선택된 1종 이상이고; 상기 y는 0.1-10의 실수인 것을 특징으로 하는 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법. According to claim 1,
the first metal is palladium, the second metal is copper, and the third metal is platinum;
The second metal precursor is at least one selected from the group consisting of Cu(NO 3 ) 2 , Cu(NO 3 ) 2· xH 2 O and CuCl 2 ; wherein x is a real number of 0.1-10;
The third metal precursor is at least one selected from the group consisting of H 2 PtCl 6 , H 2 PtCl 6· yH 2 O and K 2 PtCl 6 ; Wherein y is a carbon-supported core-shell structure alloy particle catalyst, characterized in that the real number of 0.1-10.
상기 (b) 단계의 환원반응은 수소, 암모니아, 아르곤 및 질소로 이루어진 군에서 선택되는 1종 이상의 기체 분위기에서 수행되는 것을 특징으로 하는 탄소-담지 코어-쉘 구조 합금입자 촉매의 제조방법. According to claim 1,
The reduction reaction of step (b) is a method for producing a carbon-supported core-shell structured alloy particle catalyst, characterized in that it is carried out in at least one gas atmosphere selected from the group consisting of hydrogen, ammonia, argon and nitrogen.
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