KR20230031528A - Catalyst complex for carbon dioxide reduction - Google Patents

Catalyst complex for carbon dioxide reduction Download PDF

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KR20230031528A
KR20230031528A KR1020210113867A KR20210113867A KR20230031528A KR 20230031528 A KR20230031528 A KR 20230031528A KR 1020210113867 A KR1020210113867 A KR 1020210113867A KR 20210113867 A KR20210113867 A KR 20210113867A KR 20230031528 A KR20230031528 A KR 20230031528A
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carbon dioxide
dioxide reduction
cuo
reduction catalyst
copper
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KR102608353B1 (en
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권영국
이호정
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울산과학기술원
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    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C07C11/04—Ethylene
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    • C25B3/00—Electrolytic production of organic compounds
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    • C25B3/26—Reduction of carbon dioxide
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Abstract

The present invention relates to a catalyst complex for carbon dioxide reduction, and more specifically, to a catalyst complex for carbon dioxide reduction, capable of electrochemically reducing carbon dioxide to produce ethylene and maintaining the oxidation state of copper (Cu) in a partially positively charged state. The catalyst complex for carbon dioxide reduction comprises copper oxide particles; and copper oxide aluminum particles interfacially bonded with the copper oxide particles.

Description

이산화탄소 환원 촉매 복합체{CATALYST COMPLEX FOR CARBON DIOXIDE REDUCTION}Carbon dioxide reduction catalyst complex {CATALYST COMPLEX FOR CARBON DIOXIDE REDUCTION}

본 발명은 이산화탄소 환원 촉매 복합체에 관한 것으로, 보다 상세하게 전기화학적으로 이산화탄소를 환원하여 에틸렌을 생성할 수 있으며, 구리(Cu)의 산화수를 부분 양전하 상태로 유지시킬 수 있는 이산화탄소 환원 촉매 복합체에 관한 것이다.The present invention relates to a carbon dioxide reduction catalyst complex, and more particularly, to a carbon dioxide reduction catalyst complex capable of electrochemically reducing carbon dioxide to produce ethylene and maintaining the oxidation number of copper (Cu) in a partially positively charged state. .

온실가스인 이산화탄소(CO2)를 저감하는 방법으로, 초기에는 CO2를 포집하여 저장하는 CCS(Carbon Capture and Storage) 기술이 연구되었으나, CO2 저장 공간의 한계가 존재하며, 생태계에 영향을 미친다는 단점이 존재한다. 따라서, 이를 대신하여 CO2를 유용한 물질로 전환하는 CCU(Carbon Capture and Utilization) 기술에 대한 연구가 활발히 진행되고 있다. 다양한 CCU 기술 중 전기화학적 CO2 전환 기술은 신재생 에너지와 직접 연계가 가능한고 스케일업(Scale-up)이 용이한 장점을 가지고 있다. 또한, 일산화탄소(CO), 개미산(HCOOH) 뿐 아니라 에틸렌(C2H4)나 에탄올(C2H5OH) 등의 고부가가치 생성물을 수득할 수 있어 주목을 받고 있다.As a method of reducing carbon dioxide (CO 2 ), which is a greenhouse gas, CCS (Carbon Capture and Storage) technology for capturing and storing CO 2 was initially studied, but CO 2 storage space is limited and it affects the ecosystem. has a downside. Therefore, instead of this, research on carbon capture and utilization (CCU) technology for converting CO 2 into useful substances is being actively conducted. Among various CCU technologies, electrochemical CO 2 conversion technology has the advantage of being directly linked to renewable energy and being easy to scale-up. In addition, carbon monoxide (CO), formic acid (HCOOH), as well as high value-added products such as ethylene (C 2 H 4 ) or ethanol (C 2 H 5 OH) can be obtained, attracting attention.

종래의 실증화된 전기화학적 CO2 전환 기술은 대부분 Syngas(CO)와 수소의 혼합 가스) 또는 HCOOH를 대상으로 하였다. 그러나, 이들은 시장 규모와 확장성이 제한되므로 에틸렌과 같은 고부가가치 생성물을 얻는 실증화된 기술이 필요하다. 에틸렌은 석유화학 산업에서 다양한 고분자 물질을 생산하는데 이용되는 기초 유분으로, '석유화학산업의 쌀'이라는 별칭을 가지고 있다. 그러나, 기존의 에틸렌 생산공정은 대량의 CO2가 생성되므로, 장기적으로 이를 대체할 공정이 필요하다. 전기화학적 CO2 전환 기술을 통해 에틸렌을 생산하면 이산화탄소를 저감할 뿐 아니라, 기존의 환경파괴적인 공정을 대체할 수 있다.Conventional empirical electrochemical CO 2 conversion technologies are mostly targeted at syngas (CO) and hydrogen mixed gas) or HCOOH. However, since they are limited in market size and scalability, a demonstrated technology for obtaining high value-added products such as ethylene is required. Ethylene is a basic oil used to produce various polymer materials in the petrochemical industry, and has the nickname 'rice of the petrochemical industry'. However, since the existing ethylene production process produces a large amount of CO 2 , a long-term replacement process is required. Ethylene production through electrochemical CO 2 conversion technology not only reduces carbon dioxide, but can also replace existing environmentally destructive processes.

전기화학적 CO2 전환을 통해 에틸렌 등의 C2+ 생성물을 형성하기 위해서는 먼저 CO가 형성된 후, 이들의 이합체화(dimerization) 반응이 일어나야 한다. 구리(Cu)는 전기화학적 CO2 전환을 통해 C2+ 생성물을 얻을 수 있는 유일한 금속 촉매이다. 이는 구리가 전기화학적 CO2 전환 반응의 핵심 중간체인 표면에 흡착된 일산화탄소(*CO)에 대하여 최적의 흡착에너지(binding energy)를 가지고 있기 때문이다. 따라서 Cu 촉매의 여러 특성을 조절하여 고효율로 에틸렌을 생성하는 연구가 진행되고 있다.In order to form C 2+ products such as ethylene through electrochemical CO 2 conversion, CO must first be formed, followed by a dimerization reaction thereof. Copper (Cu) is the only metal catalyst capable of obtaining C 2+ products through electrochemical CO 2 conversion. This is because copper has an optimal binding energy for carbon monoxide (*CO) adsorbed on the surface, which is a key intermediate in the electrochemical CO 2 conversion reaction. Therefore, research is being conducted to produce ethylene with high efficiency by controlling various characteristics of the Cu catalyst.

대한민국 등록특허 제10-1973002호Republic of Korea Patent No. 10-1973002

본 발명의 목적은 이산화탄소를 환원시켜 전기화학적으로 전환시킬 수 있는 촉매 복합체를 제공하는 것으로, 보다 상세하게는, 산화구리(CuOx) 촉매 입자 내 구리(Cu)의 산화수를 부분 양전하 상태로 유지시킬 수 있는 이산화탄소 환원 촉매를 제공하는 것이다. An object of the present invention is to provide a catalyst composite capable of electrochemically converting carbon dioxide by reducing it, and more specifically, to maintain the oxidation number of copper (Cu) in copper oxide (CuO x ) catalyst particles in a partially positively charged state. It is to provide a carbon dioxide reduction catalyst capable of

상기 목적을 달성하기 위하여, 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체는 산화구리 입자; 및 상기 산화구리 입자와 계면 접합된 산화구리알루미늄 입자를 포한다.In order to achieve the above object, a carbon dioxide reduction catalyst composite according to an embodiment of the present invention includes copper oxide particles; and copper aluminum oxide particles interfacially bonded to the copper oxide particles.

상기 이산화탄소 환원 촉매 복합체는 이산화탄소를 에틸렌으로 전기화학적으로 전환시키는 것일 수 있다.The carbon dioxide reduction catalyst complex may electrochemically convert carbon dioxide into ethylene.

상기 산화구리 입자는 CuO일 수 있다.The copper oxide particles may be CuO.

상기 산화구리알루미늄 입자는 상기 산화구리 입자 내 구리(Cu)의 산화수를 제어하는 것일 수 있으며, 상기 산화구리알루미늄 입자는 Al2CuO4일 수 있다.The copper aluminum oxide particle may control the oxidation number of copper (Cu) in the copper oxide particle, and the copper aluminum oxide particle may be Al 2 CuO 4 .

상기 이산화탄소 환원 촉매 복합체는 구리(Cu)와 알루미늄(Al)의 총함량 100 wt%를 기준으로 알루미늄(Al)의 함량이 9 내지 32 wt%일 수 있다.The carbon dioxide reduction catalyst composite may have an aluminum (Al) content of 9 to 32 wt% based on 100 wt% of the total content of copper (Cu) and aluminum (Al).

상기 이산화탄소 환원 촉매 복합체는, CuO/Al2CuO4일 수 있다.The carbon dioxide reduction catalyst complex may be CuO/Al 2 CuO 4 .

본 발명의 이산화탄소 환원 촉매 복합체는 이산화탄소의 환원을 통한 전기화학전 전환 시 에틸렌을 생성하는 효과가 있다.The carbon dioxide reduction catalyst complex of the present invention has an effect of generating ethylene during electrochemical conversion through reduction of carbon dioxide.

또한, 본 발명의 이산화탄소 환원 촉매 복합체는 구리(Cu)의 산화수를 부분 양전하 상태로 유지시킴으로써 이산화탄소의 환원 촉매 활성을 향상시키는 효과가 있다.In addition, the carbon dioxide reduction catalyst complex of the present invention has an effect of improving the carbon dioxide reduction catalytic activity by maintaining the oxidation number of copper (Cu) in a partially positively charged state.

도 1은 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체의 TEM 이미지를 도시한 것이다.
도 2는 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체의 SEM EDS mapping 이미지 분석 결과를 도시한 것이다.
도 3은 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체의 XRD(X-Ray powder Diffraction) 분석 결과를 도시한 것이다.
도 4는 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체의 XPS(X-ray Photoelectron Spectroscopy) 분석 결과를 도시한 것이다.
도 5a 내지 도 5d는 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체 및 비교예로서 상용 Cu foil에 대한 전기화학적 수계 반응의 분석 결과를 도시한 것이다.
도 6은 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체의 XANES(X-ray absorption near edge structure) 분석 결과를 도시한 것이다.
도 7a 내지 도 7c는 본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체 및 비교예로서 상용 CuO에 대하여 전기화학적 기상계 반응의 분석 결과를 도시한 것이다.1 shows a TEM image of a carbon dioxide reduction catalyst composite according to an embodiment of the present invention.
Figure 2 shows the results of SEM EDS mapping image analysis of the carbon dioxide reduction catalyst composite according to an embodiment of the present invention.
Figure 3 shows the results of XRD (X-Ray powder diffraction) analysis of the carbon dioxide reduction catalyst complex according to an embodiment of the present invention.
4 shows the result of XPS (X-ray Photoelectron Spectroscopy) analysis of the carbon dioxide reduction catalyst complex according to an embodiment of the present invention.
5A to 5D show analysis results of an aqueous electrochemical reaction for a carbon dioxide reduction catalyst composite according to an embodiment of the present invention and a commercial Cu foil as a comparative example.
6 illustrates an X-ray absorption near edge structure (XANES) analysis result of a carbon dioxide reduction catalyst composite according to an embodiment of the present invention.
7A to 7C show analysis results of an electrochemical vapor phase reaction with respect to a carbon dioxide reduction catalyst composite according to an embodiment of the present invention and commercially available CuO as a comparative example.

이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

본 발명의 일 실시예에 따른 이산화탄소 환원 촉매 복합체는 산화구리 입자; 및 상기 산화구리 입자와 계면 접합된 산화구리알루미늄 입자를 포한다.A carbon dioxide reduction catalyst composite according to an embodiment of the present invention includes copper oxide particles; and copper aluminum oxide particles interfacially bonded to the copper oxide particles.

이산화탄소(CO2)는 탄소의 가장 산화된 상태이므로, CO2를 다른 물질로 변환하는 유일한 방법은 환원시키는 것이다. 또한, CO2는 매우 안정적인 물질이므로, 이를 환원시키기 위해서는 큰 에너지가 필요하다. 따라서, 전기화학적 CO2 전환 반응은 상당히 negative한 potential 하에서 진행되며, 이러한 강한 환원 분위기는 전기화학적 CO2 전환 반응 중 촉매 표면을 환원시킬 수 있으며, 산화구리 촉매(CuO 또는 Cu2O) 단독 사용 시 반응 중에 촉매가 Cu(0)으로 환원되어 CO 환원 활성이 감소된다. 따라서, 산화구리 촉매를 기반으로 다양한 방법을 통해 반응 중 Cu의 산화수를 부분 양전하(partially positive) 상태로 유지하는 것이 필요하다.Since carbon dioxide (CO 2 ) is the most oxidized form of carbon, the only way to convert CO 2 to other substances is to reduce it. In addition, since CO 2 is a very stable substance, a large amount of energy is required to reduce it. Therefore, the electrochemical CO 2 conversion reaction proceeds under a significantly negative potential, and this strong reducing atmosphere can reduce the catalyst surface during the electrochemical CO 2 conversion reaction, and when a copper oxide catalyst (CuO or Cu 2 O) is used alone During the reaction, the catalyst is reduced to Cu(0), reducing the CO reduction activity. Therefore, it is necessary to maintain the oxidation number of Cu in a partially positive state during the reaction through various methods based on a copper oxide catalyst.

상기 이산화탄소 환원 촉매 복합체는 이산화탄소를 에틸렌으로 전기화학적으로 전환시키는 것일 수 있다. 상기 이산화탄소 환원 촉매 복합체는 이산화탄소 환원 반응시 에틸렌 페러데이(FE) 효율을 향상시키는 것으로서, 이산화탄소의 환원 시 에틸렌으로 선택도를 향상시키는 것이다.The carbon dioxide reduction catalyst complex may electrochemically convert carbon dioxide into ethylene. The carbon dioxide reduction catalyst composite improves ethylene Faraday (FE) efficiency during carbon dioxide reduction reaction, and improves selectivity to ethylene during carbon dioxide reduction.

구리(Cu)의 산화수(oxidation state)는 CO의 환원에 큰 영향을 주는 요소이며, 반응에 참여하는 촉매 표면의 Cu(0)는 residual bridge adsorbed CO (CObridge)를 형성한다. CObridge는 프로톤 부가 반응(protonation)이 잘 일어나지 않아 탄화수소(hydrocarbon)의 형성이 제한되기 때문에 CObridge만 존재한다면 CO가 주요 생성물이 된다. 한편, Cu(1)은 atop adsorbed CO(COatop)을 형성하며, COatop은 프로톤 부가 반응(protonation)이 활발히 일어나기 때문에 COatop만 존재한다면 CH4가 주요 생성물이 된다. Cu(0)와 Cu(1)이 혼재하여 CObridge와 COatop이 동시 형성되면 그들의 시너지 효과(synergetic effect)에 의해 CO-CO 또는 CO-CHO 등의 이합체화(dimerization)반응의 활성화 에너지 장벽(activation energy barrier)이 낮아져 C2+생성물의 선택도가 향상된다. 따라서, 전기화학적 CO2 전환을 통해 에틸렌(C2H4)을 생성하기 위해서는 촉매 표면 Cu의 산화수를 부분 양전하 상태(Cu(0)와 Cu(1)이 혼재한 상태)로 만들필요가 있다.The oxidation state of copper (Cu) is a factor that greatly affects the reduction of CO, and Cu(0) on the catalyst surface participating in the reaction forms a residual bridge adsorbed CO (CO bridge ). Since the formation of hydrocarbons is limited because the proton addition reaction does not occur in the CO bridge , CO is the main product if only the CO bridge exists. On the other hand, Cu(1) forms atop adsorbed CO (CO atop ), and since CO atop actively undergoes protonation, CH 4 becomes the main product if only CO atop is present. When Cu(0) and Cu(1) are mixed to form CO bridge and CO atop at the same time, their synergistic effect causes the activation energy barrier of dimerization reaction such as CO-CO or CO-CHO ( activation energy barrier) is lowered and the selectivity of the C 2+ product is improved. Therefore, in order to produce ethylene (C 2 H 4 ) through electrochemical CO 2 conversion, it is necessary to make the oxidation number of Cu on the catalyst surface into a partially positively charged state (a state in which Cu(0) and Cu(1) are mixed).

상기 산화구리 입자는 CuO일 수 있으며, 이산화탄소의 전기화학적 전환을 통해 에틸렌을 형성하기 위하여 구리(Cu) 산화수가 부분 양전하인 상태인 것이며, Cu(0)와 Cu(1)이 혼재된 상태일 수 있다. The copper oxide particles may be CuO, and in order to form ethylene through the electrochemical conversion of carbon dioxide, the oxidation number of copper (Cu) is in a partially positively charged state, and Cu (0) and Cu (1) may be mixed. there is.

상기 산화구리알루미늄 입자는 Al2CuO4일 수 있으며, 상기 산화구리 입자 내 구리(Cu)의 산화수를 제어하는 것일 수 있으며, 보다 상세하게는 상기 산화구리알루미늄 입자는 이산화탄소 환원 촉매 복합체의 구리(Cu)의 산화수를 부분 양전하 상태로 유지시키 위한 것이다.The copper aluminum oxide particles may be Al 2 CuO 4 , and may control the oxidation number of copper (Cu) in the copper oxide particles. More specifically, the copper aluminum oxide particles may be copper (Cu) of the carbon dioxide reduction catalyst complex. ) is to maintain the oxidation number of the partial positive charge.

상기 이산화탄소 환원 촉매 복합체는, CuO/Al2CuO4일 수 있다.The carbon dioxide reduction catalyst complex may be CuO/Al 2 CuO 4 .

상기 이산화탄소 환원 촉매 복합체는 구리(Cu)와 알루미늄(Al)의 총함량 100 wt%를 기준으로 구리(Cu)의 함량은 68 내지 91 wt%일 수 있으며, 알루미늄(Al)의 함량이 9 내지 32 wt%일 수 있으며, 바람직하게는 구리(Cu)의 함량은 77 wt%이며, 알루미늄(Al) 원소의 함량이 23 wt%일 수 있다.The carbon dioxide reduction catalyst composite may have a copper (Cu) content of 68 to 91 wt% and an aluminum (Al) content of 9 to 32 wt% based on 100 wt% of the total content of copper (Cu) and aluminum (Al). It may be wt%, preferably, the content of copper (Cu) is 77 wt%, and the content of aluminum (Al) element may be 23 wt%.

본 발명의 일 실시예에 따른 이산화탄소 환원 복합체의 경우, 알루미늄(Al)의 함량(wt%)이 너무 적으면 촉매 표면 구리(Cu)의 산화수 유지를 용이하게 할 만큼 알루미늄(Al) 양이 충분치 않아 반응 중 Cu(0)으로 환원되어 CO2 환원 반응의 활성이 감소된다. 또한, 알루미늄(Al) 함량(wt%)이 너무 많으면, 과량의 알루미늄(Al)이 활성점인 Cu와 CO2의 접촉을 방해하여 전기화학적 CO2 전환 반응 보다는 수소 생성 반응 (Hydrogen evolution reaction, HER)을 촉진시킨다. 따라서, 구리(Cu)와 알루미늄(Al)의 비율(wt%)이 최적화된 이산화탄소 환원 촉매 복합체를 제공함으로써 CO2의 환원이 촉진되어 에틸렌 선택도가 향상될 수 있다.In the case of the carbon dioxide reduction composite according to an embodiment of the present invention, if the content (wt%) of aluminum (Al) is too small, the amount of aluminum (Al) is not sufficient to facilitate maintaining the oxidation number of copper (Cu) on the surface of the catalyst. During the reaction, it is reduced to Cu(0) and the activity of the CO 2 reduction reaction is reduced. In addition, if the aluminum (Al) content (wt%) is too large, the excess aluminum (Al) interferes with the contact between Cu, which is an active site, and CO 2 , resulting in a hydrogen evolution reaction (HER) rather than an electrochemical CO 2 conversion reaction. ) promotes Accordingly, by providing a carbon dioxide reduction catalyst composite in which the ratio (wt%) of copper (Cu) and aluminum (Al) is optimized, reduction of CO 2 may be promoted and ethylene selectivity may be improved.

상기 이산화탄소 환원 촉매 복합체는 공동 침전(coprecipitation) 방법에 의하여 제조되는 것일 수 있으며, 구리 전구체와 알루미늄 전구체를 이용하여 이산화탄소 환원 촉매 복합제를 제조하는 것일 수 있다. 상기 구리 전구체는 질산 구리(Cu(NO3)2)일 수 있으며, 상기 알루미늄 전구체는 질산알루미늄(Al(NO3)3)일 수 있다.The carbon dioxide reduction catalyst complex may be prepared by a co-precipitation method, and the carbon dioxide reduction catalyst complex may be prepared using a copper precursor and an aluminum precursor. The copper precursor may be copper nitrate (Cu(NO 3 ) 2 ), and the aluminum precursor may be aluminum nitrate (Al(NO 3 ) 3 ).

이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 본 실시예는 본 발명의 이해를 위한 하나의 실시예일 뿐이며, 본 발명의 범위를 제한하는 것은 아니다. Hereinafter, the present invention will be described in more detail through examples. This embodiment is only one example for understanding the present invention, and does not limit the scope of the present invention.

실시예 1. Example 1.

3 g의 질산구리(Cu(NO3)2)와 1 g의 질산알루미늄(Al(NO3)3)을 과량의 탈이온수(DI water)에 용해시켜 제1 용액을 제조한다. 제1 용액의 질산구리 몰(mol) 수의 2 배에 해당하는 탄산암모늄((NH4)2CO3) 3.1 g을 탈이온 수에 용해시켜 제2 용액을 제조한다. 제1 용액과 제2 용액의 혼합 용액을 핫 플레이트(hot plate)에서 50℃로 3 시간(h) 동안 교반(stirring) 시키면서 반응시킨다. 반응이 완료된 혼합 용액을 상온에서 2 시간(h) 동안 침전시킨 후 여과(filtration)하여 수득된 고체를 60℃의 오븐에서 하루(24h) 동안 건조시킨다. 건조시킨 고체를 관상로(tube furnace)에서 가열속도(ramping rate) 3 ℃/min으로 800 ℃에서 5 시간(h) 동안 하소(calcination)시킨 후, 노냉(furnace cooling) 하여 이산화탄소 환원 촉매 복합체(구리-알루미늄 합금) 분말(powder)을 수득한다.A first solution is prepared by dissolving 3 g of copper nitrate (Cu(NO 3 ) 2 ) and 1 g of aluminum nitrate (Al(NO 3 ) 3 ) in an excess of DI water. A second solution is prepared by dissolving 3.1 g of ammonium carbonate ((NH 4 ) 2 CO 3 ) twice the number of moles of copper nitrate in the first solution in deionized water. The mixed solution of the first solution and the second solution is reacted while stirring for 3 hours (h) at 50° C. on a hot plate. The reaction-completed mixed solution is precipitated at room temperature for 2 hours (h), and then the solid obtained by filtration is dried in an oven at 60° C. for one day (24 h). The dried solid was calcined at 800 ° C. for 5 hours (h) at a ramping rate of 3 ° C./min in a tube furnace, followed by furnace cooling to obtain a carbon dioxide reduction catalyst complex (copper -Aluminum alloy) powder is obtained.

실시예 2.Example 2.

실시예 1과 동일하게 실시하되, 3 g의 질산알루미늄을 이용하였다.It was carried out in the same manner as in Example 1, but 3 g of aluminum nitrate was used.

실시예 3.Example 3.

실시예 1과 동일하게 실시하되, 5 g의 질산알루미늄을 이용하였다.It was carried out in the same manner as in Example 1, but 5 g of aluminum nitrate was used.

실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체의 제조시 질산구리, 질산알루미늄, 탄산암모늄의 혼합비를 하기 표 1에 정리하였다.The mixing ratio of copper nitrate, aluminum nitrate, and ammonium carbonate in the preparation of the carbon dioxide reduction catalyst complex according to Examples 1 to 3 is summarized in Table 1 below.

질산구리copper nitrate 질산알루미늄aluminum nitrate 탄산암모늄Ammonium Carbonate 실시예 1Example 1 3 g3g 1 g1 g 3.1 g3.1g 실시예 2Example 2 3 g3g 3 g3g 3.1 g3.1g 실시예 3Example 3 3 g3g 5 g5g 3.1 g3.1g

실험예 1. 합성촉매 구조 특성 확인Experimental Example 1. Confirmation of the structural characteristics of the synthetic catalyst

실시예 3에 따른 이산화탄소 환원 촉매 복합체의 TEM 이미지를 분석하여 도 1에 도시하였다. A TEM image of the carbon dioxide reduction catalyst composite according to Example 3 was analyzed and shown in FIG. 1 .

도 1을 참조하면, CuO와 Al2CuO4가 각각 형성되었음을 확인할 수 있으며, CuO와 Al2CuO4 사이의 계면간 접합된 것을 확인할 수 있으며, 계면을 기준으로 경계를 형성하고 있음을 확인할 수 있다.Referring to FIG. 1, it can be confirmed that CuO and Al 2 CuO 4 are formed, respectively, and it can be confirmed that the interface between CuO and Al 2 CuO 4 is bonded, and that a boundary is formed based on the interface. .

실시예 3에 따른 이산화탄소 환원 촉매 복합체의 SEM EDS mapping 이미지 분석 결과를 도 2에 도시하였다.The results of SEM EDS mapping image analysis of the carbon dioxide reduction catalyst complex according to Example 3 are shown in FIG. 2 .

도 2를 참조하면, Cu, O, Al 각각의 원소가 균일하게 분포되어 있음을 확인할 수 있다.Referring to FIG. 2 , it can be seen that elements of Cu, O, and Al are uniformly distributed.

실험예 2. 원소 질량분석Experimental Example 2. Elemental Mass Spectrometry

실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체에 대하여 ICP-MS(Inductively Coupled Plasma-Mass Spectrometry) 분석을 통하여 Cu와 Al에 대한 질량을 분석하였으며, 분석 결과를 하기 표 2에 정리하였다.For the carbon dioxide reduction catalyst composites according to Examples 1 to 3, the mass of Cu and Al was analyzed through ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) analysis, and the analysis results are summarized in Table 2 below.

Cu 함량Cu content Al 함량Al content 실시예 1Example 1 91 wt%91wt% 9 wt%9wt% 실시예 2Example 2 77 wt%77wt% 23 wt%23wt% 실시예 3Example 3 68 wt%68wt% 32 wt%32wt%

실험예 3. XRD 분석Experimental Example 3. XRD analysis

실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체의 XRD(X-Ray powder Diffraction) 분석 결과를 도 3에 도시하였다. 도 3에서 실시예 1에 따른 이산화탄소 환원 촉매 복합체는 'CuO/Al2CuO4-9'로 명명하며, 실시예 2에 따른 이산화탄소 환원 촉매 복합체는 'CuO/Al2CuO4-23'로 명명하며, 실시예 3에 따른 이산화탄소 환원 촉매 복합체는 'CuO/Al2CuO4-32'로 명명하였다.The results of XRD (X-Ray powder diffraction) analysis of the carbon dioxide reduction catalyst complex according to Examples 1 to 3 are shown in FIG. 3 . In FIG. 3, the carbon dioxide reduction catalyst composite according to Example 1 is referred to as 'CuO/Al 2 CuO 4 -9', and the carbon dioxide reduction catalyst composite according to Example 2 is named 'CuO/Al 2 CuO 4 -23'. , The carbon dioxide reduction catalyst composite according to Example 3 was named 'CuO/Al 2 CuO 4 -32'.

도 3을 참조하면, 비교데이터로서, CuO의 XRD 분석결과를 함께 포함하고 있으며, 실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체는 모두 CuO에 해당하는 피크(peak)(2θ) 및 Al2CuO4에 해당하는 피크(peak)(2θ)가 관찰되는 것을 확인할 수 있으며, 실시예 2에 따른 이산화탄소 환원 촉매 복합체('CuO/Al2CuO4-23')는 CuO에 해당하는 피크(peak)(2θ) 35.495˚(d-spacing 0.253 nm; -111 phase) 및 38.686˚ (d-spacing 0.232 nm; 111 phase)가 관찰되는 것을 확인할 수 있으며, Al2CuO4에 해당하는 피크(peak)(2θ) 31.262˚ (d-spacing 0.2863 nm 220 phase) 및 36.835˚ (d-spacing 0.24386 nm; 311 phase))가 관찰되는 것을 확인할 수 있다. 실시예 1 및 3에 따른 이산화탄소 환원 촉매 복합체의 경우에도 실시예 2에 따른 이산화탄소 환원 촉매 복합체와 동일한 CuO 피크와 Al2CuO4 피크를 가지는 것을 확인할 수 있다. 이를 통하여, 실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체는 'CuO'와 'Al2CuO4'가 각각 존재하는 복합체임을 확인할 수 있다.Referring to FIG. 3, as comparative data, the XRD analysis results of CuO are included together, and the carbon dioxide reduction catalyst composites according to Examples 1 to 3 are all peaks (2θ) corresponding to CuO and Al 2 CuO 4 It can be seen that a peak (2θ) corresponding to is observed, and the carbon dioxide reduction catalyst composite ('CuO/Al 2 CuO 4 -23') according to Example 2 has a peak (2θ) corresponding to CuO. ) 35.495˚ (d-spacing 0.253 nm; -111 phase) and 38.686˚ (d-spacing 0.232 nm; 111 phase) are observed, and the peak corresponding to Al 2 CuO 4 (2θ) 31.262 It can be seen that ˚ (d-spacing 0.2863 nm 220 phase) and 36.835˚ (d-spacing 0.24386 nm; 311 phase)) are observed. It can be seen that the carbon dioxide reduction catalyst composite according to Examples 1 and 3 also has the same CuO peak and Al 2 CuO 4 peak as the carbon dioxide reduction catalyst composite according to Example 2. Through this, it can be confirmed that the carbon dioxide reduction catalyst composite according to Examples 1 to 3 is a composite in which 'CuO' and 'Al 2 CuO 4 ' respectively exist.

실험예 4. XPS 분석Experimental Example 4. XPS analysis

실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체의 XPS(X-ray Photoelectron Spectroscopy) 분석 결과를 도 4에 도시하였다. 도 4에서 실시예 1에 따른 이산화탄소 환원 촉매 복합체는 'CuO/Al2CuO4-9'로 명명하며, 실시예 2에 따른 이산화탄소 환원 촉매 복합체는 'CuO/Al2CuO4-23'로 명명하며, 실시예 3에 따른 이산화탄소 환원 촉매 복합체는 'CuO/Al2CuO4-32'로 명명하며, 비교예로서 산화구리를 'CuO'로 명명하였다.The results of XPS (X-ray Photoelectron Spectroscopy) analysis of the carbon dioxide reduction catalyst complex according to Examples 1 to 3 are shown in FIG. 4 . In FIG. 4, the carbon dioxide reduction catalyst composite according to Example 1 is referred to as 'CuO/Al 2 CuO 4 -9', and the carbon dioxide reduction catalyst composite according to Example 2 is designated as 'CuO/Al 2 CuO 4 -23'. , The carbon dioxide reduction catalyst complex according to Example 3 was named 'CuO/Al 2 CuO 4 -32', and copper oxide was named 'CuO' as a comparative example.

도 4의 (a)는 Cu 2p 피크(peak)를 도시한 것이며, 도 4의 (b)는 Al 2p 피크(peak)를 도시한 것이다.(a) of FIG. 4 shows the Cu 2p peak, and (b) of FIG. 4 shows the Al 2p peak.

도 4의 (a)를 참조하면, Cu 2p 피크에서 실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체는 비교예('CuO') 보다 높은 결합 에너지(Binding Energy)에 위치하는 것을 확인할 수 있으며, Al 함량이 높은 수록(실시예 1에서 실시예 3으로 갈수록) 보다 많은 이동(shift)가 일어남을 확인할 수 있다.Referring to (a) of FIG. 4, it can be confirmed that the carbon dioxide reduction catalyst composite according to Examples 1 to 3 in the Cu 2p peak is located at a higher binding energy than the comparative example ('CuO'), and Al It can be seen that the higher the content (from Example 1 to Example 3), the more shifts occur.

도 4의 (b)를 참조하면, Al 2p 피크에서 Al 함량이 낮을수록(실시예 3에서 실시예 1로 갈수록) 낮은 결합 에너지(Binding Energy)에 위치하는 것을 확인할 수 있다.Referring to (b) of FIG. 4, it can be seen that the lower the Al content in the Al 2p peak (from Example 3 to Example 1), the lower the binding energy.

도 4를 참조하면, Cu 2p과 Al 2p 피크의 결과 모두 Cu에서 Al로 전하 이동(charge transger)이 일어남을 확인할 수 있다. 이는 실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체에서의 활성점(active site)은 Cu이며, Al은 Cu의 산화수를 조절하는 역할을 하는 것으로, Cu의 전자를 Al이 받아줌으로써, Cu의 산화수를 부분적 양전하(partially positive) 상태로 만들 수 있음을 알 수 있다.Referring to FIG. 4 , it can be confirmed that charge transfer from Cu to Al occurs in both Cu 2p and Al 2p peak results. This means that the active site in the carbon dioxide reduction catalyst complex according to Examples 1 to 3 is Cu, and Al plays a role in controlling the oxidation number of Cu. It can be seen that it can be made into a partially positive state.

실험예 5. COExperimental Example 5. CO 22 환원 수계 반응 reducing water-based reaction

실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체 및 비교예로서 상용 Cu foil에 대하여 전기화학적 CO2 전환 반응을 수계 반응으로 수행하였으며, 그 결과를 각각 도 5a 내지 도 5d에 도시하였다. 도 5a는 실시예 1('CuO/Al2CuO4-9')에 대한 결과를 도시한 것이며, 도 5b는 실시예 2('CuO/Al2CuO4-23')에 대한 결과를 도시한 것이며, 도 5c는 실시예 3('CuO/Al2CuO4-32')에 대한 결과를 도시한 것이며, 도 5d는 비교예('Cu Foil')에 대한 결과를 도시한 것이다.An electrochemical CO 2 conversion reaction was performed in an aqueous reaction for the carbon dioxide reduction catalyst composite according to Examples 1 to 3 and commercial Cu foil as a comparative example, and the results are shown in FIGS. 5A to 5D, respectively. FIG. 5A shows the results for Example 1 ('CuO/Al 2 CuO 4-9 '), and FIG. 5B shows the results for Example 2 ('CuO/Al 2 CuO 4-23 '). 5c shows the results for Example 3 ('CuO/Al 2 CuO 4 -32'), and FIG. 5d shows the results for the comparative example ('Cu Foil').

도 5a 내지 도 5c의 수계반응은, 3 전극 H-type cell을 활용하였고, Ag/AgCl을 기준 전극으로, Pt foil을 상대전극으로 사용하였다. 작업 전극으로는 GCE(glassy carbon electrode)를 사용하였으며, 실시예 1 내지 3에 따른 촉매 로딩(loading) 양이 0.6 mg/cm2이 되도록 촉매 잉크(ink)를 작업 전극 위에 드롭 캐스팅(drop-casting) 하였으며, 촉매 잉크는 촉매(실시예 1 내지 3) 분말(powder) 2 mg, 에탄올(ethanol) 1 mL 및 Nafion 117 함유 용액 40 μL를 이용하여 제작하였으며, 제작된 촉매 잉크 300 μL씩 작업 전극 위에 로딩(loading) 하였다. 전해질로는 0.1 M KHCO3를 사용하였으며, 이온교환막으로는 Selemion을 사용하였다. 전기화학적 CO2 전환 반응을 진행하기 전에 약 20분 간 CO2를 purge 하여 전해질을 CO2 saturation 시켰으며, Faradaic efficiency(FE) 분석을 위해서 Chronoamperometry mode(정전압법)로 반응을 진행하였다.In the aqueous reaction of FIGS. 5A to 5C, a three-electrode H-type cell was utilized, and Ag/AgCl was used as a reference electrode and Pt foil was used as a counter electrode. A glassy carbon electrode (GCE) was used as the working electrode, and catalyst ink was drop-casting on the working electrode so that the catalyst loading amount according to Examples 1 to 3 was 0.6 mg/cm 2 . ), and the catalyst ink was prepared using 2 mg of catalyst powder (Examples 1 to 3), 1 mL of ethanol, and 40 μL of a solution containing Nafion 117, and 300 μL of the prepared catalyst ink was placed on the working electrode. Loading was done. 0.1 M KHCO 3 was used as the electrolyte, and Selemion was used as the ion exchange membrane. Before proceeding with the electrochemical CO 2 conversion reaction, CO 2 was purged for about 20 minutes to saturate the electrolyte with CO 2 , and the reaction was conducted in chronoamperometry mode (constant voltage method) for faradaic efficiency (FE) analysis.

도 5d는 3 전극 H-type cell을 활용하였고, Ag/AgCl을 기준 전극으로, Pt foil을 상대전극으로 사용하였다. 작업 전극으로는 상용 Cu Foil을 이용하였다. 전해질로는 0.1 M KHCO3를 사용하였으며, 이온교환막으로는 Selemion을 사용하였다. 전기화학적 CO2 전환 반응을 진행하기 전에 약 20분 간 CO2를 purge 하여 전해질을 CO2 saturation 시켰으며, Faradaic efficiency(FE) 분석을 위해서 Chronoamperometry mode(정전압법)로 반응을 진행하였다.5d shows that a three-electrode H-type cell was used, and Ag/AgCl was used as a reference electrode and Pt foil was used as a counter electrode. A commercially available Cu Foil was used as the working electrode. 0.1 M KHCO 3 was used as the electrolyte, and Selemion was used as the ion exchange membrane. Before proceeding with the electrochemical CO 2 conversion reaction, CO 2 was purged for about 20 minutes to saturate the electrolyte with CO 2 , and the reaction was conducted in chronoamperometry mode (constant voltage method) for faradaic efficiency (FE) analysis.

기체상 생성물을 분석하기 위해서 Online Gas Chromatography(GC)를 사용하였고, 시간에 따라 3번 분석하여 평균값을 사용하였으며, 최대 값과 최소 값은 error bar로 표시하였다. 또한, 액체상 생성물을 분석하기 위해서 High-Performance Liquid Chromatography(HPLC)를 사용하였고, 반응이 끝난 후 생성물을 3번 분석하여 평균값을 사용하였으며, 최대 값과 최소 값은 error bar로 표시하였다.Online Gas Chromatography (GC) was used to analyze the gaseous product, and the average value was used by analyzing three times according to time, and the maximum and minimum values were displayed as error bars. In addition, High-Performance Liquid Chromatography (HPLC) was used to analyze the liquid phase product, and after the reaction was completed, the product was analyzed three times and the average value was used, and the maximum and minimum values were displayed as error bars.

도 5a 내지 도 5c를 참조하면, 실시예 1 내지 3에 따른 이산화탄소 환원 촉매 복합체에서 구리(Cu)와 알루미늄(Al)의 비율(중량)을 조절하여 비교한 것으로, 도 5a 내지 도 5d를 참조하면, 상용 Cu foil(비교예)에 비하여, CO2 환원을 통한 C2H4(에틸렌) 전환율이 개선되는 것을 확인할 수 있으며, 보다 상세하게는, 상용 Cu Foil의 에틸렌 FE 25%(도 5d)를 실시예 2('CuO/Al2CuO4-23')을 사용하여 최대 81%로 개선시키는 것을 확인할 수 있다.Referring to Figures 5a to 5c, the ratio (weight) of copper (Cu) and aluminum (Al) in the carbon dioxide reduction catalyst composite according to Examples 1 to 3 was adjusted and compared. Referring to Figures 5a to 5d , Compared to commercial Cu foil (Comparative Example), it can be seen that the C 2 H 4 (ethylene) conversion rate through CO 2 reduction is improved. More specifically, ethylene FE 25% of commercial Cu Foil (FIG. 5d) It can be seen that the improvement is up to 81% using Example 2 ('CuO/Al2CuO4-23').

또한, 도 5a를 참조하면, 실시예 1에 따른 이산화탄소 환원 촉매 복합체의 경우, Al의 함량이 낮으며, 이에 따라서, 구리의 산화수를 용이하게 유지할 수 있을 정도의 Al의 양이 충분하지 않아 Cu(0)으로 환원되어 CO 환원 반응 활성이 감소된다. 즉, CO가 C2H4로 더 이상 환원되지 않으며 수계반응시 일부가 CO로 방출된다.In addition, referring to FIG. 5A, in the case of the carbon dioxide reduction catalyst composite according to Example 1, the content of Al is low, and accordingly, the amount of Al is not sufficient to easily maintain the oxidation number of copper, so Cu ( 0), reducing the activity of the CO reduction reaction. That is, CO is no longer reduced to C 2 H 4 and some of it is released as CO during aqueous reaction.

또한, 도 5b를 참조하면, 실시예 2에 따른 이산화탄소 환원 촉매 복합체의 경우, 최적의 Cu-Al 비율을 가지는 것이므로 C2H4 선택성이 우수하다.Also, referring to FIG. 5B , in the case of the carbon dioxide reduction catalyst composite according to Example 2, since it has an optimal Cu-Al ratio, the C 2 H 4 selectivity is excellent.

또한, 도 5c를 참조하면, Al의 함량이 높으며, 이에 따라서 Al이 활성점인 Cu와 CO2의 접촉을 방해하여 HER을 촉진시킨다. 즉, H2의 비율이 상대적(실시예 1 및 2에 비하여)으로 높다.In addition, referring to FIG. 5C , the content of Al is high, and accordingly, Al interferes with the contact between Cu, which is an active site, and CO 2 to promote HER. That is, the ratio of H 2 is relatively high (compared to Examples 1 and 2).

실험예 6. XANES 분석Experimental Example 6. XANES analysis

실시예 2에 따른 이산화탄소 환원 촉매 복합체의 XANES(X-ray absorption near edge structure) 분석을 수행하였으며, 이와 함께 비교예로서, CuO에 대한 XANES 분석을 함께 수행하였으며, 각각의 분석 결과를 도 6에 도시하였다.X-ray absorption near edge structure (XANES) analysis was performed on the carbon dioxide reduction catalyst composite according to Example 2, and as a comparative example, XANES analysis on CuO was also performed, and each analysis result is shown in FIG. 6 did

도 6에서, 'Before reaction'은 실시예 2 및 비교예에서의 촉매 복합체 합성 직후의 XAFS(X-ray Absorption Fine Structure) 분석을 통해 얻은 XANES 결과이며, 'After reaction'은 실시예 2 및 비교예에서 합성된 촉매 복합체를 각각 실험예 5의 수계 반응을 90 분(min) 동안 수행한 후의 XAFS 분석을 통해 얻은 XANES 결과이다.In FIG. 6, 'Before reaction' is the XANES result obtained through XAFS (X-ray Absorption Fine Structure) analysis immediately after the synthesis of the catalyst complex in Example 2 and Comparative Example, and 'After reaction' is Example 2 and Comparative Example These are the XANES results obtained through XAFS analysis after performing the water-based reaction of Experimental Example 5 for 90 minutes (min), respectively, for the catalyst complex synthesized in .

비교예('CuO')에 대한 분석 결과를 도 6의 (a)에 도시하였으며, 실시예 2('CuO/Al2CuO4-23')에 따른 이산화탄소 환원 촉매 복합체의 분석 결과를 도 6의 (b)에 도시하였다.The analysis result for the comparative example ('CuO') is shown in (a) of FIG. 6, and the analysis result of the carbon dioxide reduction catalyst complex according to Example 2 ('CuO/Al 2 CuO 4 -23') is shown in FIG. It is shown in (b).

도 6을 참조하면, 비교예('CuO')의 경우에는 전기화학적 CO2 전환반응 이후 촉매 표면이 Cu(0)으로 환원되는 반면, 실시예 2('CuO/Al2CuO4-23')에 따른 이산화탄소 환원 촉매 복합체는 산화수를 유지하는 것을 확인할 수 있다.Referring to FIG. 6, in the case of the comparative example ('CuO'), the catalyst surface is reduced to Cu(0) after the electrochemical CO 2 conversion reaction, whereas in Example 2 ('CuO/Al 2 CuO 4 -23') It can be confirmed that the carbon dioxide reduction catalyst complex according to maintains the oxidation number.

실험예 7. COExperimental Example 7. CO 22 환원 기상계 반응 Reduction weather system reaction

실시예 2에 따른 이산화탄소 환원 촉매 복합체 및 비교예로서 상용 CuO에 대하여 전기화학적 CO2 전환 반응을 기상계 반응으로 수행하였으며, 수행 결과를 도 7a 내지 도 7c에 도시하였다. 도 7a는 실시예 2에 따른 이산화탄소 환원 촉매 복합체('CuO/Al2CuO4-23')에 대한 기상계 반응 분석 결과(페러데이 효율(FE) 계산 결과)를 도시한 것이며, 도 7b는 비교예는 상용 구리산화물('Commercial CuO')에 대한 기상계 반응 분석 결과(페러데이 효율(FE) 계산 결과)를 도시한 것이며, 도 7c는 실시예 2('CuO/Al2CuO4-23') 및 비교예('Commercial CuO')의 분석에 따른 에틸렌(C2H4)의 부분 전류밀도의 비교 결과를 도시한 것이다.An electrochemical CO 2 conversion reaction was performed with respect to the carbon dioxide reduction catalyst complex according to Example 2 and commercially available CuO as a comparative example in a gas phase reaction, and the performance results are shown in FIGS. 7a to 7c. FIG. 7A shows the result of gas-phase reaction analysis (Faraday efficiency (FE) calculation result) for the carbon dioxide reduction catalyst complex ('CuO/Al 2 CuO 4-23 ') according to Example 2, and FIG. 7B is a comparative example. shows the gas-phase reaction analysis result (Faraday efficiency (FE) calculation result) for commercial copper oxide ('Commercial CuO'), and FIG. 7c shows Example 2 ('CuO/Al 2 CuO 4 -23') and It shows the comparison result of the partial current density of ethylene (C 2 H 4 ) according to the analysis of the comparative example ('Commercial CuO').

도 7a 및 도 7b의 기상계 반응은, 3 전극 flow-type cell을 활용하였고, Hg/HgO를 기준 전극으로, Ni-Fe-Mo 합금을 상대전극으로 사용하였다. 작업 전극으로는 GDE(gas diffusion electrode)를 사용하였으며, 실시예 2에 따른 촉매 로딩(loading) 양이 0.6 mg/cm2이 되도록 촉매 잉크(ink)를 작업 전극 위에 스프레이 코팅(spray-coating) 하였으며, 촉매 잉크(ink)는 촉매(실시예 2) 분말(powder) 50 mg, 에탄올(ethanol) 20 mL 및 Nafion 117 함유 용액 313 μL를 이용하여 제작하였으며, 제작된 촉매 잉크의 로링(loading) 양이 0.6 mg/cm2이 되도록 작업 전극 위에 로딩 loading 하였다. 전해질로는 1 M KOH를 사용하였으며, 이온교환막으로는 sustanion을 사용하였다. FE 분석을 위해 Chronopotentiometry mode(정전류법)로 전기화학적 CO2 전환 반응을 진행하였다. 7a and 7b, a three-electrode flow-type cell was utilized, and Hg/HgO was used as a reference electrode and a Ni-Fe-Mo alloy was used as a counter electrode. A gas diffusion electrode (GDE) was used as the working electrode, and catalyst ink was spray-coated on the working electrode so that the catalyst loading amount according to Example 2 was 0.6 mg/cm 2 , catalyst ink was prepared using 50 mg of catalyst (Example 2) powder, 20 mL of ethanol, and 313 μL of a solution containing Nafion 117, and the loading amount of the prepared catalyst ink 0.6 mg/cm 2 It was loaded on the working electrode so that it was loaded. 1 M KOH was used as the electrolyte, and sustanion was used as the ion exchange membrane. For FE analysis, an electrochemical CO 2 conversion reaction was performed in chronopotentiometry mode (galvanostatic method).

기체상 생성물을 분석하기 위해서 Online Gas Chromatography(GC)를 사용하였고, 시간에 따라 3번 분석하여 평균값을 사용하였으며, 최대 값과 최소 값은 error bar로 표시하였다. 또한, 액체상 생성물을 분석하기 위해서 High-Performance Liquid Chromatography (HPLC)를 사용하였고, 반응이 끝난 후 electrolyte를 3번 분석하여 평균값을 사용하였으며, 최대 값과 최소 값은 error bar로 표시하였다.Online Gas Chromatography (GC) was used to analyze the gaseous product, and the average value was used by analyzing three times according to time, and the maximum and minimum values were displayed as error bars. In addition, High-Performance Liquid Chromatography (HPLC) was used to analyze the liquid phase product, and after the reaction was completed, the electrolyte was analyzed three times and the average value was used, and the maximum and minimum values were displayed as error bars.

도 7a 내지 도 7c를 참조하면, 기상계 반응에서는 상용 CuO의 에틸렌 부분 전류밀도 102.06 mA/cm2를 실시예 2('CuO/Al2CuO4-23')을 사용하여 최대 437.68 mA/cm2로 개선하는 것을 확인할 수 있다.Referring to FIGS. 7a to 7c, in the gas phase reaction, the ethylene partial current density of commercial CuO was 102.06 mA/cm 2 up to 437.68 mA/cm 2 using Example 2 ('CuO/Al 2 CuO 4 -23'). improvement can be seen.

이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also made according to the present invention. falls within the scope of the rights of

Claims (7)

산화구리 입자; 및
상기 산화구리 입자와 계면 접합된 산화구리알루미늄 입자를 포함하는,
이산화탄소 환원 촉매 복합체.
copper oxide particles; and
Including copper aluminum oxide particles interfacially bonded with the copper oxide particles,
Carbon Dioxide Reduction Catalyst Complex.
 제1항에 있어서,
이산화탄소를 에틸렌으로 전기화학적으로 전환시키는 것인,
이산화탄소 환원 촉매 복합체.
According to claim 1,
the electrochemical conversion of carbon dioxide to ethylene,
Carbon Dioxide Reduction Catalyst Complex.
 제1항에 있어서,
상기 산화구리 입자는 CuO인 것인,
이산화탄소 환원 촉매 복합체.
According to claim 1,
The copper oxide particles are CuO,
Carbon Dioxide Reduction Catalyst Complex.
 제1항에 있어서,
상기 산화구리알루미늄 입자는 상기 산화구리 입자 내 구리(Cu)의 산화수를 제어하는 것인,
이산화탄소 환원 촉매 복합체.
According to claim 1,
The copper aluminum oxide particles control the oxidation number of copper (Cu) in the copper oxide particles,
Carbon Dioxide Reduction Catalyst Complex.
 제1항에 있어서,
상기 산화구리알루미늄 입자는 Al2CuO4인 것인,
이산화탄소 환원 촉매 복합체.
According to claim 1,
The copper aluminum oxide particles are Al 2 CuO 4 That is,
Carbon Dioxide Reduction Catalyst Complex.
 제1항에 있어서,
상기 이산화탄소 환원 촉매 복합체는 구리(Cu)와 알루미늄(Al)의 총함량 100 wt%를 기준으로 알루미늄(Al)의 함량이 9 내지 32 wt%인 것인,
이산화탄소 환원 촉매 복합체.
According to claim 1,
The carbon dioxide reduction catalyst composite has an aluminum (Al) content of 9 to 32 wt% based on 100 wt% of the total content of copper (Cu) and aluminum (Al),
Carbon Dioxide Reduction Catalyst Complex.
 제1항에 있어서,
상기 이산화탄소 환원 촉매 복합체는,
CuO/Al2CuO4인 것인,
이산화탄소 환원 촉매 복합체.
According to claim 1,
The carbon dioxide reduction catalyst complex,
Which is CuO/Al 2 CuO 4 ,
Carbon Dioxide Reduction Catalyst Complex.
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