• 청정기술
• /
• 제30권1호
• /
• pp.55-61
• /
• 2024

연료전지의 산소환원반응용 백금 촉매의 높은 비용을 극복하기 위하여 나노 구조 제어를 통한 고성능의 백금 합금 촉매 개발 연구가 활발히 수행되고 있다. 본 연구에서는 탄소에 담지된 니켈-니켈 질화물 복합체와 백금 이온 간의 갈바닉 치환 반응 시 용액의 pH 조절을 통한 촉매의 나노구조를 중공형이나 코어-쉘 구조로 제어하는 방법을 제시하였다. X선 회절 분석과 투과전자현미경, 유도결합 플라즈마를 이용한 분석을 통해 합성 조건에 따른 금속의 상태와 함량 및 합금 입자의 형상에 대한 물리적 특성 평가를 수행하였다. 제조된 촉매를 산소환원반응 촉매로 적용하였으며 상용 백금 촉매 대비 1.7배(중공형 촉매) 및 1.9배(코어-쉘 구조 촉매) 개선된 전기화학적 활성 면적 당 활성을 나타내었다.

• Journal of Electrochemical Science and Technology
• /
• 제7권4호
• /
• pp.298-305
• /
• 2016

The development of non-precious metal based electrocatalysts is highly desired for the oxygen reduction reaction (ORR) as alternates to noble metal based ORR electrocatalysts. Herein, we report mononulcear copper(II) complex $[CuLbpy]ClO_4$ (L=4-[(2-hydroxyphenylimino)methyl]benzoic acid) containing poly(allylamine.HCl) polymer (PAlACuLbpy) as an electrocatalyst for oxygen reduction reaction (ORR). PAlACuLbpy was mixed with poly(acrylic acid) and tetraethylortho silicate to prepare a composite and then deposited on the screen printed electrode surface. The modified electrode (PAlACuLbpy/PCE) is highly stable and showed a quasi-reversible redox behavior with $E_{1/2}=-0.2V$ vs. Ag/AgCl(3 M KCl) in 0.1 M phosphate buffer at pH 7 under argon atmosphere. PAlACuLbpy/PCE exhibited a remarkable ORR activity with an onset potential of -0.1 V vs Ag/AgCl in 0.1 M PB (pH 7) in the presence of oxygen. The kinetics for ORR was studied by rotating disk voltammetry in neutral aqueous medium and the results indicated that the number of electrons involving in the ORR is four and the conversion products are water and hydrogen peroxide.

• 청정기술
• /
• 제20권3호
• /
• pp.269-276
• /
• 2014

본 연구는 수은연속측정시스템의 가장 중요한 구성 요소의 하나인 산화수은을 원소수은으로 환원시킬 수 있는 건식 환원촉매시스템 개발을 목적으로 수행되었다. 산화-환원 표준전위를 기준으로 산화수은의 원소수은으로의 환원반응을 자발적으로 일으킬 수 있는 촉매 대상물질로 Fe, Cu, Ni 및 Co 4종류의 전이금속이 선택되었다. 이들 전이금속 촉매들은 산소가 없는 반응가스 조성에서 산화수은의 원소수은으로의 환원반응에 대해 높은 활성을 보였다. 그러나 산소가 존재하는 경우 환원 활성이 크게 감소하는데 이는 산소에 의해 해당 전이금속이 산화수은 환원 활성이 낮은 전이금속산화물로 변환되기 때문이다. 반응가스에 산소가 존재하여도 수소를 공급하면 산화수은 환원 활성이 크게 증가되는데 이는 산화수은의 환원반응이 진행되는 고온에서 산소와 수소 사이의 연소반응에 의해 산소가 소모되기 때문으로 확인되었다. Fe를 환원촉매로 하고 배기가스에 수소를 공급하는 산화수은 환원촉매시스템은 $SnCl_2$ 수용액을 사용하는 습식화학 환원기술에 필적할 수준의 활성을 나타내기 때문에 상업적으로 적용 가능한 산화수은 환원시스템으로 기대된다.

• Journal of Electrochemical Science and Technology
• /
• 제11권3호
• /
• pp.220-237
• /
• 2020

Modern electrochemical energy devices involve generation and reduction of fuel gases through electrochemical reactions of water splitting, alcohol oxidation, oxygen reduction, etc. Initially, these processes were executed in the presence of noble metal-based catalyst that showed low overpotential and high current density. However, its high cost, unavailability, corrosion and related toxicity limited its application. The search for alternative with high stability, durability, and efficiency led scientists towards carbon nanoparticles supported catalysts which has high surface area, good electrical conductivity, tunable morphology, low cost, ease of synthesis and stability. Carbon nanoparticles are classified into two groups based on morphology, one and zero dimensional particles. Carbon nanoparticles at zero dimension, denoted as carbon dots, are less used carbon support compared to other forms. However, recently carbon dots with improved electronic properties have become popular as catalyst as well as catalyst support. This review focused on the recent advances in electrocatalytic activities of carbon dots. The mechanisms of common electrocatalytic reactions and the role of the catalysts are also discussed. The review also proposed future developments and other research directions to overcome current limitations.

• Journal of Electrochemical Science and Technology
• /
• 제8권3호
• /
• pp.169-182
• /
• 2017

Iron and nitrogen codoped carbon (Fe-N/C) catalysts have emerged as one of the most promising replacements for state-of-the-art platinum-based electrocatalysts for oxygen reduction reaction (ORR) in polymer electrolyte fuel cells. During the last decade, significant progress has been achieved in Fe-N/C catalysts in terms of ORR activity improvement and active site identification. In this review, we focus on recent efforts towards advancing our understanding of the structure of active sites in Fe-N/C catalysts. We summarize the spectroscopic and electrochemical methods that are used to analyze active site structure in Fe-N/C catalysts, and the relationship between active site structure and ORR activity in these catalysts. We provide an overview of recently reported synthetic strategies that can generate active sites in Fe-N/C catalysts preferentially. We then discuss newly suggested active sites in Fe-N/C catalysts. Finally, we conclude this review with a brief future outlook.

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

• Bulletin of the Korean Chemical Society
• /
• 제16권5호
• /
• pp.392-397
• /
• 1995

o-Phenylenediamine (o-PD) was electropolymerized on glassy carbon electrodes under a potential cycling condition. The resulting polymer films mediated electrons for the reduction of molecular oxygen at pH=1.0. It was found from the RDE, RRDE, and cyclic voltammetry experiments that the modified electrodes reduce oxygen to hydrogen peroxide at about 300 mV lower potential than the bare glassy carbon electrode. The polymer film consisted of more than two components. Among those, only one component was active in oxygen reduction, which was formed mainly in the earlier stage of the electropolymerization. 2,3-Diaminophenazine, a cyclic dimer of o-PD, was also active in the oxygen reduction reaction, from which it was suggested that the active polymeric component has a structural unit similar to the cyclic dimer. Finally, the electropolymerization mechanism for the formation of the active and inactive components has been proposed.

• 한국수소및신에너지학회논문집
• /
• 제22권2호
• /
• pp.213-222
• /
• 2011

To check adaptability of low ash coal(hyper coal) to chemical looping combustion, reaction characteristics of two coals (Roto and Hyper coal) with two oxygen carriers (NiO/bentonite, OCN703-1100) have been investigated in a thermogravimetric analyzer. Hyper coal represented low combustion rate and high ignition temperature, high volatile content and high devolatilization rate, and therefore, showed worse oxygen transfer during successive 10 cycle reduction-oxidation test than Roto coal. Finally we selected Roto coal as the candidate coal for chemical looping combustion. For Roto coal, OCN703-1100 particle showed better oxygen transfer than NiO/bentonite particle. During 10 cycle reduction oxidation test, change of the extent of oxidation (Wo) was negligible and we could conclude that both oxygen carriers have sufficient regeneration ability.

• 한국신재생에너지학회:학술대회논문집
• /
• 한국신재생에너지학회 2007년도 춘계학술대회
• /
• pp.129-132
• /
• 2007

Advanced structure of metal-supported solid oxide fuel cells was devised to overcome sealing problem and mechanical instability in ceramic-supported solid oxide fuel cells. STS430 whose dimensions were 26mm diameter, 1mm thickness and 0.4mm channel width was used as metal support. Thin ceramic layer composed of anode(Ni/YSZ) and electrolyte(YSZ) was joined with STS430 metal support by using a cermet adhesive. $La_{0.8}Sr_{0.2}Co_{0.4}Mn_{0.6}O_{3}$ perovskite oxide was used as cathode material. It was noted that oxygen reduction reaction of cathode governed the overall cell performance from oxygen partial pressure dependance.

• 한국수소및신에너지학회논문집
• /
• 제32권1호
• /
• pp.41-52
• /
• 2021

NiO and Co3O4-doped porous La(CoNi)O3 perovskite oxides were prepared from excess Ni addition by a hydrothermal method using porous silica template, and characterized as bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for Zn-air rechargeable batteries in alkaline solution. Excess Ni induced to form NiO and Co3O4 in La(CoNi)O3 particles. The NiO and Co3O4-doped porous La(CoNi)O3 showed high specific surface area, up to nine times of conventionally synthesized perovskite oxide, and abundant pore volume with similar structure. Extra added Ni was partially substituted for Co as B site of ABO3 perovskite structure and formed to NiO and Co3O4 which was highly dispersed in particles. Excess Ni in La(CoNi)O3 catalysts increased OER performance (259 mA/㎠ at 2.4 V) in alkaline solution, although the activities (211 mA/㎠ at 0.5 V) for ORR were not changed with the content of excess Ni. La(CoNi)O3 with excess Ni showed very stable cyclability and low capacity fading rate (0.38 & 0.07 ㎶/hour for ORR & OER) until 300 hours (~70 cycles) but more excess content of Ni in La(CoNi)O3 gave negative effect to cyclability.