• Journal of Advanced Marine Engineering and Technology
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• 제23권3호
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• pp.389-397
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• 1999

Recently the use of Pd catalyst have been continued to expand because of cost avaliabilityand performance advantages. Especially the Pd+Rh catalyst instead of the Pt+Rh catalyst had been used for most of three way catalysts because of the more stringent emission standards and its higher temperature effectiveness. The main purpose of this study is to investigate the design parameter impacts on the Pd+Rh cat-alyst for the automotive exhaust catalysts application. This study was investigated on the catalyst efficiency for the volume and the precious metal loading of the Pd+Rh ceramic monolithic cata-lyst. And experiments concerning the effects of volume and precious metal loading on Pd+Rh three way catalysts were conducted to examined the catalyst light-off temperature and conver-sion efficiency on higher volume demonstrated almost similar performance. But their effects on higher precious metal loading demonstrated considerably better performance.

• Journal of Electrochemical Science and Technology
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• 제15권2호
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• pp.207-219
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• 2024

Metal-N-C (MNC) catalysts have been anticipated as promising candidates for oxygen reduction reaction (ORR) to achieve low-cost polymer electrolyte membrane fuel cells. The structure of the M-N_x moiety enabled a high catalytic activity that was not observed in previously reported transition metal nanoparticle-based catalysts. Despite progress in non-precious metal catalysts, the low density of active sites of MNCs, which resulted in lower single-cell performance than Pt/C, needs to be resolved for practical application. This review focused on the recent studies and methodologies aimed to overcome these limitations and develop an inexpensive catalyst with excellent activity and durability in an alkaline environment. It included the possibility of non-precious metals as active materials for ORR catalysts, starting from Co phthalocyanine as ORR catalyst and the development of methodologies (e.g., metal-coordinated N-containing polymers, metal-organic frameworks) to form active sites, M-N_x moieties. Thereafter, the motivation, procedures, and progress of the latest research on the design of catalyst morphology for improved mass transport ability and active site engineering that allowed the promoted ORR kinetics were discussed.

• Journal of Electrochemical Science and Technology
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• 제14권2호
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• pp.105-119
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• 2023

The electrochemical chlorine evolution reaction (CER) is an important electrochemical reaction and has been widely used in chlor-alkali electrolysis, on-site generation of ClO^-, and Cl₂-mediated electrosynthesis. Although precious metal-based mixed metal oxides (MMOs) have been used as CER catalysts for more than half a century, they intrinsically suffer from a selectivity problem between the CER and parasitic oxygen evolution reaction (OER). Hence, the design of selective CER electrocatalysts is critically important. In this review, we provide an overview of the fundamental issues related to the electrocatalysis of the CER and design strategies for selective CER electrocatalysts. We present experimental and theoretical methods for assessing the active sites of MMO catalysts and the origin of the scaling relationship between the CER and the OER. We discuss kinetic analysis methods to understand the kinetics and mechanisms of CER. Next, we summarize the design strategies for new CER electrocatalysts that can enhance the reactivity of MMO-based catalysts and overcome their scaling relationship, which include the doping of MMO catalysts with foreign metals and the development of non-precious metal-based catalysts and atomically dispersed metal catalysts.

• Korean Chemical Engineering Research
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• 제60권1호
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• pp.151-158
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• 2022

고가의 귀금속 촉매는 고분자 전해질 연료전지의 상업화에 걸림돌로 인식되어 저가의 비귀금속 촉매 연구가 활발하다. 본 연구에서는 Fe-N-C 촉매를 킬레이팅이 가능한 4가지 다른 질소 전구체 N,N,N',N'-detramethylethylenediamine(TMEDA), 1,2-ethylenediamine (EDA), m-dicyanobenzene (DCB), dicyandiamide (DCDA)를 이용하여 700, 800, 900, 1000 ℃에서 합성하였다. 촉매의 물리적 특성은 주사전자현미경, X선 회절분석기, 자동원소분석기를 이용하여 분석하였다. 이를 통해 촉매 표면 형태 및 원소의 분산도와 에너지 분산형 X-선 분광을 적용하여 Fe의 함량을 확인하였다. 또한 비금속 원소의 함량과 Fe의 담지 여부 등을 확인하였다. 전기화학적 특성은 순환 전압전류법과 선형주사전위법을 통해 촉매의 전기화학적 산소 환원에 대한 활성과 전자전달수 등을 분석하였다. 결과에 따르면 질소 전구체로 EDA를 사용하여 800 ℃의 소성온도에서 합성한 촉매가 가장 높은 산소 환원 활성을 보였다. 이 연구 결과는 고가의 귀금속을 대체하기 위한 노력에 도움이 될 것으로 예상된다.

• 전기화학회지
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• 제23권4호
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• pp.90-96
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• 2020

수소의 화학반응 에너지를 직접 전기 에너지로 변환하는 Polymer electolyte membrane fuel cells (PEMFCs)는 친환경 미래 운송수단 에너지원의 한 종류이다. PEMFCs의 내부에 산소 환원 반응이 매우 느리고 고가의 백금을 사용하기 때문에 이를 대체하려는 연구가 국내외에서 매우 활발히 연구되고 있다. 하지만 백금이외에 값싼 재료를 이용한 촉매의 경우 여전히 성능이 매우 상이하며 활성 향상에 대한 지표 등이 다양하다. 이에 본 총설은 non-precious metal catalyst (NPMC)의 활성 지표 등을 정리하고 최근 5년간의 자료를 요약하였다. 이를 통해 촉매재료의 선별, 합성시 주안점, 조촉매 등을 설명하며, 촉매 활성에 대한 연구의 필요성을 상기 시킬 수 있다. 이를 통해 귀금속 촉매가 널리 사용되는 분야에 적용할 수 있는 NPMC의 연구 및 개발에 기여할 수 있을 것으로 보인다. 또한 향후 연구개발의 최종적인 목표를 기술한다.

• Environmental Engineering Research
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• 제10권3호
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• pp.131-137
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• 2005

The catalytic activity of precious metals(Rh, Pd, Pt) and nickel catalysts supported on ${\gamma}-Al_2O_3\;and\;CeO_2$ in the partial combustion of methane(PCM) to syngas was investigated based on the product distribution in a fixed bed now reactor under atmospheric condition and also on analysis results by SEM, XPS, TPD, BET, and XRD. The activity of the catalysts based on the syngas yield increased in the sequence $Rh(5)/CeO_2{\geq}Ni(5)/CeO_2>>Rh(5)/Al_2O_3>Pd(5)/Al_2O_3>Ni(5)/Al_2O_3$. Compared to the precious catalysts, the syngas yield and stability of the $Ni(5)/CeO_2$ catalyst were almost similar to $(5)/CeO_2$ catalyst, and superior to these of any other catalysts. The syngas yield of $Ni(5)/CeO_2$ catalyst was 90.66% at 1023 K. It could be suggested to be the redox cycle of the successive reaction and formation of active site, $Ni^{2-}$ and the lattice oxygen, $O^{2-}$ produced due to reduction of $Ce^{4-}$ to $Ce^{3-}$.

• 한국태양에너지학회:학술대회논문집
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• 한국태양에너지학회 2012년도 춘계학술발표대회 논문집
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• pp.406-409
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• 2012

Recently, enormous research efforts have been focused on the development of non-precious catalysts to replace Pt for electrocatalytic oxygen reduction reaction (ORR), and to reduce the cost of proton exchange membrane fuel cells (PEMFCs). In recent years, heteroatom (N, B, and P) doped carbon nanostructures have been received enormous importance as a non-precious electrode materials for oxygen reduction. Doping of foreign atom into carbon is able to modify electronic properties of carbon materials. In this study, nitrogen and boron doped carbon nanostructures were synthesized by using a facile and cost-effective thermal annealing route and prepared nanostructures were used as a non-precious electrocatalysts for the ORR in alkaline electrolyte. The nitrogen doped carbon nanocapsules (NCNCs) exhibited higher activity than that of a commercial Pt/C catalyst, excellent stability and resistance to methanol oxidation. The boron-doped carbon nanostructure (BC) prepared at $900^{\circ}C$ showed higher ORR activity than BCs prepared lower temperature (800, $700^{\circ}C$). The heteroatom doped carbon nanomaterials could be promising candidates as a metal-free catalysts for ORR in the PEMFCs.

• Journal of Ceramic Processing Research
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• 제19권6호
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• pp.499-503
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• 2018

In this paper, cobalt embedded in nitrogen and sulfur co-doped carbon nanotubes (CoNSTs) were synthesized for oxygen reduction reaction (ORR) catalysts. The CoNSTs were prepared through a facile heat treatment method without any templates. Different amounts of the metal salt were employed to examine the physicochemical and electrochemical properties of the CoNSTs. The CoNSTs showed the bamboo-like tube morphology with the encased Co nanoparticles in the tubes. Through the x-ray photoelectron spectroscopy analysis, the catalysts exhibited different chemical states of the nitrogen and sulfur species. As a result, the CoNST performed high activity toward the ORR in an acidic condition with the onset potential of 0.863 V (vs. reversible hydrogen electrode). It was clearly demonstrated from the electrochemical characterizations that the quality of the nitrogen and sulfur species significantly influences the ORR activity rather than the total amount of the dopants.

• 전기화학회지
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• 제16권1호
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• pp.52-58
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• 2013

고분자 전해질 연료전지(Polymer Electrolyte Membrane Fuel Cell, PEMFC) 상용화를 위해 해결해야 할 과제 중의 하나인 가격 저감을 이루기 위한 방법으로 백금 촉매를 대신할 비귀금속(non-precious metal) 촉매 제조에 관한 연구를 수행하였다. 비귀금속 촉매의 합성은 산소환원반응(oxygen reduction reaction, ORR)의 활성점으로 알려져 있는 코발트-질소(Co-N) 결합을 형성하기 위해 질소를 포함하는 폴리아닐린(PANI)과 코발트염(Co precursor), 그리고 카본 블랙(C)을 일정한 비율대로 혼합한 후 특별한 열처리 과정 없이 단순한 화학적 환원법에 제조되었다. 제조된 Co-PANI-C 복합 촉매의 구조 분석을 위해 X-선 회절분석(X-ray diffraction, XRD)과 열중량분석(thermogravimetric analysis, TGA)을 실시하였고, ORR에 대한 활성을 평가하기 위해 rotating disk electrode(RDE) 및 rotating ring disk electrode(RRDE) 측정을 수행하였다. 그 결과 Co-PANI-C 복합 촉매는 ORR반응에 대한 개시 전압은 백금 촉매보다 60 mV 밖에 낮지 않은 값을 보였지만, 반응에 의해 발생되는 환원 전류는 여전히 백금 촉매보다 낮은 값을 보였다. 이 밖에도 전극 회전 속도에 따른 ORR 특성 변화, 전압 사이클 회수에 따른 내구성 변화, 연료전지 적용 시 성능 변화에 대해 논의할 것이다.

• Journal of Electrochemical Science and Technology
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• 제12권1호
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• pp.137-145
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• 2021

Among the non-precious metal catalysts, iron-nitrogen doped carbon (Fe-N/C) catalysts have been recognized as the most promising candidates for an alternative to Pt-based catalysts for the oxygen reduction reaction (ORR) under alkaline and acidic conditions. In this study, the nano replication method using mesoporous silica, which features tunable primary particle sizes and shape, is employed to prepare the mesoporous Fe-N/C catalysts with different shapes. Platelet SBA-15, irregular KIT-6, and spherical silica particle (SSP) were selected as a template to generate three different kinds of shapes of the mesoporous Fe-N/C catalyst. Physicochemical properties of mesoporous Fe-N/C catalysts are characterized by using small-angle X-ray diffraction, nitrogen adsorption-desorption isotherms, and scanning electron microscopy images. According to the electrochemical evaluation, there is no morphological preference of mesoporous Fe-N/C catalysts toward the ORR activity with half-cell configuration under alkaline electrolyte. By implementing X-ray photoelectron spectroscopy analysis of Fe and N atoms in the mesoporous Fe-N/C catalysts, it is possible to verify that the activity towards ORR highly depends on the portions of "Fe-N" species in the catalysts regardless of the shape of catalysts. It was suggested that active site distribution in the Fe-N/C is one important factor towards ORR activity.