• Proceedings of the Korea Water Resources Association Conference
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• 2012.05a
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• pp.477-477
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• 2012

미생물 연료전지는 정부가 추진하고 있는 신성장 동력사업의 녹색성장 정책에 부합하는 환경융합 신기술로써 일상생활에서 배출되는 하 폐수와 같은 유기물질을 전자공여체로 이용하여 전기에너지를 생산 할 수 있다는 점에서 각광받고 있다. 미생물 연료전지는 산화전극부의 미생물이 공급된 유기물질 을 분해하여 전자와 수소이온을 생성시키며 이들은 산소가 존재하는 환원전극부로 이동하여 물로 환원 됨 으로써 전기를 생성한다. 전기 화학적 성능의 향상을 위해 미생물 연료전지에서는 환원전극부에 서의 산소와 전자 및 수소이온의 빠른 환원반응을 유도해 주는 Pt촉매를 이용한다. 하지만 고가의 Pt 촉매는 미생물 연료전지의 현장적용을 위한 규모확장 시 초기비용이 증가되는 문제점을 초래한다. 이에 미생물 연료전지의 대체촉매 개발에 대한 많은 연구가 진행되고 있다. 화학적 연료전지에 관한 논문에서 연료전지의 촉매로 산소 환원반응에 높은 성능을 보이는 Co-N/C 형태의 Cobalt poly-pyrrole carbon가 제시 되었다. 이는 가격적인 측면에서는 Pt촉매의 약1/10배 정도 수준이지만 셀 성능은 Pt촉매의 95%정도의 효율을 보인다는 측면에서 향후 Pt 대체촉매로 가능성을 보여주는 새로운 비금속 촉매물질이다. Cobalt poly-pyrrole carbon이 Pt-catalsyt 셀 전압 성능 대비 약 66 %의 효율을 보였고 내부저항과 최대전력 밀도에 있어서도 촉매를 사용하지 않은 경우와 비금속 촉매의 성능보다 높음을 알 수 있었다. 본 연구는 Pt-catalsyt를 대체할 수 있는 저가의 산소환원 촉매물질 발굴을 위해 미생물연료전지에서 사용된 전례가 없으며 현재 화학전지의 촉매로 널리 쓰이고 있는 Cobalt poly-pyrrole carbon의 산소환원 촉매로써의 이용가능성을 평가하기 위해 실시되었으며, 평가한 결과는 첫 번째로 Cobalt poly-pyrrole carbon을 사용한 경우가 촉매를 사용하지 않은 경우와 비금속 촉매보다 환원 전극부에서의 원활한 환원작용이 진행되고 있음을 추측할 수 있으며 Pt-catalyst와 비교하였을 때 성능 대비 저렴한 가격으로 가격 경쟁력에 있어서 우월하다고 판단되었고 두 번째로 전기화학적 성능평가 및 EIS를 이용한 환원전극부의 내부저항 평가를 실시한 결과 셀 전압에 있어서 가장 많은 도말량 ($2.0mg/cm^2$)이 높은 성능을 보이고 있음을 알 수 있었다.

• Resources Recycling
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• v.18 no.5
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• pp.12-18
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• 2009

The 20% Pt/C catalysts were synthesized using the chemical reduction method for polymer electrolyte fuel cell cathode and were heat-treated in the temperature range from 300 to $600^{\circ}C$. The oxygen reduction reaction of the catalysts was evaluated using the electrochemical measurement. The oxygen reduction reaction of the heat-treated Pt/C at $300^{\circ}C$ had high catalytic activity and the oxygen reduction reaction current of that was 2 times than that of non-heat treatment catalyst. It is considered that the change of the crystallinity and particle size by heat treatment could increase the catalytic activity.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.383-385
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• 2009

비백금계 코발트 전이금속 촉매를 탄소지지체에 담지한 뒤, 암모니아 분위기에서 $500^{\circ}C$에서 3시간 동안 열처리하는 과정을 통해 코발트 질화물 촉매를 제조했다. 제조된 촉매들의 구조와 형태를 각각 XRD, HE-TEM등을 통해 분석하였고, 전위 측정기를 이용한 CV, LSV 결과로부터 촉매의 전기화학적 산소 환원특성을 분석하여, 기존의 연료전지 양극 촉매로 사용되는 고가의 백금촉매를 대체하기 위한 비백금계로서의 가능성을 확인하였다.

• Clean Technology
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• v.20 no.3
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• pp.269-276
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• 2014

This study was aimed to develop catalytic system for the dry-based reduction of oxidized mercury ($Hg^{2+}$) to elemental mercury ($Hg^0$) which is one of the most important components comprising mercury continuous emission monitoring system (Hg-CEMS). Based on the standard potential in oxidation-reduction reaction, transition metals including Fe, Cu, Ni and Co were selected as possible candidates for catalyst proceeding spontaneous reduction of $Hg^{2+}$ into $Hg^0$. These transition metal catalysts revealed high activity for reduction of $Hg^{2+}$ into $Hg^0$ in the absence of oxygen in reactant gases. However, their activities were greatly decreased in the presence of oxygen, which was attributed to the transformation of transition metals by oxygen to the corresponding transition metal oxides with less catalytic activity for the reduction of oxidized mercury. Hydrogen supplied to the reactant gases significantly enhanced $Hg^{2+}$ reduction activity even in the presence of oxygen. It might be due to occurrence of combustion reaction between $H_2$ and $O_2$ causing the consumption of $O_2$ at such high reaction temperature at which oxidized mercury reduction reaction took place. Because the system showed high activity for $Hg^{2+}$ reduction to $Hg^0$, which was compatible to that of wet-chemistry technology using $SnCl_2$ solution, the catalytic reduction system of Fe catalyst with the supply of $H_2$ could be employed as a commercial system for the reduction of oxidized mercury to elemental mercury.

• Clean Technology
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• v.30 no.1
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• pp.55-61
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• 2024

Efforts are actively underway to address the issues related to the high cost of Pt-based catalysts for oxygen reduction reactions by designing high-performance Pt-based alloys through the control of their nanostructures. In this study, a method was proposed to control the nanostructure of Pt-based alloys, either hollow or core-shell, by adjusting the pH of the solution during the galvanic replacement reaction between the carbon-supported nickel-nickel nitride composite and the Pt ions. The physical characteristics, including the state, quantity, and morphology of the metal particles under different preparation conditions, were evaluated through X-ray diffraction, transmission electron microscopy, and inductively coupled plasma. When the prepared catalysts were employed for the oxygen reduction reaction, they exhibited an improvement in area specific-activity compared to a commercial Pt/C, with a 1.7 and 1.9-fold enhancement for the hollow and core-shell structured catalysts, respectively.

• Journal of Energy Engineering
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• v.23 no.3
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• pp.157-162
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• 2014

In this research, we investigate electrical performance and electrochemical properties of carbon supported Pt (Pt/C) that is synthesized by polyol method. With the Polyol_Pt/C that is adopted for oxygen reduction reaction (ORR) as cathode of proton exchange membrane fuel cells (PEMFCs), their catalytic activity and ORR performance and electrical performance are estimated and compared with commercial Pt/C(Johnson Mattey) catalyst. Their electrochemically active surface (EAS) area are measured by cyclic voltammetry (CV), respectively. On the other hand, regarding ORR activity and electrical performance of the catalysts, (i) linear sweeping voltammetry by rotating disk electrode and (ii) PEMFC single cell tests are used. The CV measurement demonstrate EAS of Polyol_Pt/C is compared with commercial JM_Pt/C. In case of Polyol_Pt/C, its half-wave potential, kinetic current density are excellent. Based on data obtained by half-cell test, when PEMFC single cell tests are carried out, current density measured at 0.6V and maximum power density of the PEMFC single cell employing Polyol_Pt/C are better than those employing commercial Pt/C. Conclusively, Polyol_Pt/C synthesized by modified polyol process shows better ORR catalytic activity and PEMFC performance than other catalysts.

• Clean Technology
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• v.20 no.3
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• pp.212-217
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• 2014

In order to regenerate the sulfidated desulfurization sorbent, oxygen is used as the oxidant agent on the regeneration process. The small amount of oxygen un-reacted in regeneration process is flowed into direct sulfur recovery process. However, the reactivity for $SO_2$ reduction can be deteriorated with the un-reacted oxygen by various reasons. In this study, the deactivation effects of un-reacted oxygen contained in the off-gas of regeneration process flowed into direct sulfur recovery process of hot gas desulfurization system were investigated. Sn-Zr based catalysts were used as the catalyst for $SO_2$ reduction. The contents of $SO_2$ and $O_2$ contained in the regenerator off-gas used as the reactants were fixed to 5.0 vol% and 4.0 vol%, respectively. The catalytic activity tests with a Sn-Zr based catalyst were for $SO_2$ reduction performed at $300-450^{\circ}C$ and 1-20 atm. The un-reacted oxygen oxidized the elemental sulfur produced by $SO_2$ catalytic reduction and the conversion of $SO_2$ was reduced due to the production of $SO_2$. However, the temperature for the oxidation of elemental sulfur increased with increasing pressure in the catalytic reactor. Therefore, it was concluded that the decrease of reactivity at high pressure is occurred by catalytic deactivation, which is the re-oxidation of lattice oxygen vacancy in Sn-Zr based catalyst with the un-reacted oxygen on the catalysis by redox mechanism. Meanwhile the un-reacted oxygen oxidized CO supplied as the reducing agent and the temperature in the catalyst packed bed also increased due to the combustion of CO. It was concluded that the rapidly increasing temperature in the packed bed can induce the catalytic deactivation such as the sintering of active components.

• Journal of Korean Society of Environmental Engineers
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• v.38 no.5
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• pp.242-248
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• 2016

The overall reaction rate of fuel cell is governed by oxygen reduction reaction (ORR) in the cathode due to its slowest reaction compared to the oxidation of hydrogen in the anode. The ORR efficiency can be readily evaluated by examining the adsorption strength of atomic oxygen on the surface of catalysts (i.e., known as a descriptor) and the adsorption energy can be controlled by transforming the surface geometry of catalysts. In the current study, the effect of the surface geometry of catalysts (i.e., strain effect) on the adsorption strength of atomic oxygen on platinum catalysts was analyzed by using density functional theory (DFT). The optimized lattice constant of Pt ($3.977{\AA}$) was increased and decreased by 1% to apply tensile and compressive strain to the Pt surface. Then the oxygen adsorption strengths on the modified Pt surfaces were compared and the electron charge density of the O-adsorbed Pt surfaces was analyzed. As the interatomic distance increased, the oxygen adsorption strength became stronger and the d-band center of the Pt surface atoms was shifted toward the Fermi level, implying that anti-bonding orbitals were shifted to the conduction band from the valence band (i.e., the anti-bonding between O and Pt was less likely formed). Consequently, enhanced ORR efficiency may be expected if the surface Pt-Pt distance can be reduced by approximately 2~4% compared to the pure Pt owing to the moderately controlled oxygen binding strength for improved ORR.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2017.05a
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• pp.86-86
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• 2017

고효율의 에너지 변환 및 친환경적인 이점들을 이유로, 고분자전해질 연료전지(PEMFC)는 차세대 에너지 장치로 이목을 끌어왔다. 반면, 값비싼 백금 촉매의 이용은 연료전지의 상업적 이용에 주요한 결점으로 작용했다. 최근, Zelenay와 연구팀은 폴리아닐린-철-탄소 복합체구조에서 산소환원활성이 백금과 견주어 비슷한 성능을 낼 수 있음을 보고 하였다. Dodelet은 이러한 높은 성능이 전이금속의 영향에 의한 것일 수 있다는 주장을 하였다. 본 연구팀은 지난 연구에서 제일원리전산모사를 통해 니켈, 코발트, 구리등과 같은 전이금속이 질소가 도핑된 탄소 그래핀층에 미치는 거동을 밝혔다. 결론적으로, 금속들은 질소가 도핑된 그래핀의 전자구조를 바꿀 수 있고, 이러한 전자구조의 변화는 산소 환원반응에서 긍정적으로 작용할 수 있음을 확인하였다. 이러한 이론적 연구에 기반하여, 탄소층으로 감싼 금속은 내구성과 활성을 동시에 보유한 향후 전망있는 촉매 물질로 예상되어진다. 특히, 질소가 도핑된 탄소층으로 코팅된 철-코발트 합금은 계산을 통해 산소환원반응에서 우수할 것으로 예측되었다. 본 연구팀은 FeCo@N-C 나노입자를 직접 합성하였고, 이 촉매의 우수한 활성을 전기화학적, 구조적 관점에서 1) 질소의 도핑 효과, 2) 탄소의 두께 효과, 3) 합금효과에 집중하여 분석하였다.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.243.2-243.2
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• 2010

현재 바이오디젤(Bio diesel)은 유지와 메탄올을 염기촉매를 넣고 전이에스테르화(Trans-esterification)반응하여 생산한다. 생산된 1세대 바이오 디젤은 분자 내 산소가 다량 함유되어 여러 가지 단점을 가지기 때문에 전이에스테르화 반응을 대체한 탈산소(Deoxygenation)반응이 주목 받고 있다. 본 연구에서는 유리지방산(Free fatty acid, FFA)인 올레익 산(Oleic acid)의 탈산소반응을 수행하였다. 하이드로탈사이트(Hydrotalcites) 구조인 MgO-$Al_2O_3$(MgO=70 wt%)를 6시간 동안 $500^{\circ}C$에서 예비소성(Pre-calcination)하여 담체로 사용하였다. 제조된 MgO-$Al_2O_3$ 담체에 함침법(Incipient wetness method)으로 20 wt% Ni을 담지 시켰다. 제조된 Ni/MgO-$Al_2O_3$촉매는 소성온도를 변화시켜 반응 실험을 수행하였다. TPR 분석을 통해 산화-환원특성을 분석하였고 생성물의 원소분석을 통해 생성물의 산소함량을 측정하였다.