• Title/Summary/Keyword: 산화환원촉매

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Application of carbon-supported PdPt as anode catalysts in PEM fuel cell (PdPt/C 촉매의 고분자전해질 연료전지의 산화극 촉매 적용)

  • Cho, Yong-Hun;Choi, Baeck-Beom;Cho, Yoon-Hwan;Park, Hyun-Seo;Sung, Yung-Eun
    • 한국신재생에너지학회:학술대회논문집
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    • 2006.11a
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    • pp.396-398
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    • 2006
  • PdPt/C (Pd:Pt atomic ratio of around 19:1 60wt, %) 촉매를 고분자전해질 연료전지용 전극 촉매소재의 적용하였다. PdPt/C 촉매를 산화극 촉매로, 환원극 촉매로는 Pt/C 촉매를 사용하고 반대로 산화극 촉매는 Pt/C 촉매, 환원극 촉매로는 PdPt/C 촉매를 사용했을 때, PdPt/C 촉매를 산화극과 환원극 촉매로 동시에 사용했을 때의 고분자전해질 연료전지의 단위전지 성능을 각각 비교하였다. PdPt/C촉매를 산화극에만 적용했을 때에 Pt/C 상용촉매를 산화극과 환원극에 모두 적용했을 때의 성능만큼 좋은 성능을 확인할 수 있었다. 환원극 촉매는 Pt/C를 사용하고 산화극 촉매를 PdPt/C Pt/C Pd/C를 사용하였을 매의 성능을 비교하였다. Pd/C를 산화극 촉매로 사용한 단위전지가 나머지 두 경우의 성능에 비하여 현저히 떨어짐을 확인할 수 있었다. 이는 극소량의 Pt 량을 포함한 PdPt/C 촉매가 고분자전해질 연료전지의 산화극 Pt/C 촉매의 대체촉매로 사용 가능함을 보여준다.

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Catalytic Reduction of Oxidized Mercury to Elemental Form by Transition Metals for Hg CEMS (수은 연속측정시스템에서 전이금속에 의한 산화수은의 원소수은으로의 촉매환원)

  • Ham, Sung-Won
    • 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.

Redox Property of Transition Metal Oxides in Catalytic Oxidation (TPR/TPO 실험기법을 이용한 전이금속산화물의 산화-환원 특성 연구)

  • Kim, Young-Ho;Lee, Ho-In
    • Applied Chemistry for Engineering
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    • v.10 no.8
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    • pp.1161-1168
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    • 1999
  • The redox property of oxide materials of the 3rd period transition metals(Cr~Zn), V, Mo, and W was studied with temperature-programmed reduction/temperature-programmed oxidation(TPR/TPO) experiment. The peak temperatures of TPO spectra were equal to or lower than those of TPR spectra. And the peak shapes of TPO spectra were broader than those of TPR ones. The activation energies of TPR/TPO for the oxides of the 3rd period transition metals showed in the range of 33~149 kJ/mol, while for the oxides of V, Mo, and W, they showed relatively higher values. The change of activation energies of TPR/TPO with various metal oxides showed a similar trend to the change of their metal-oxygen bond strengths. The change of activation energies of o-xylene oxidation for various metal oxides was proportional to the difference (${\Delta}E_a$) between the activation energy of TPR and that of TPO. From these results, we concluded that the oxidation of o-xylene over various metal oxide catalysts follows the Mars-van Krevelen mechanism including the surface reduction-oxidation of the metal oxide itself.

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Characteristics of Adsorption, Desorption of Exhaust Gases and Deactivation of LNT and SCR Catalysts for Diesel Vehicles (디젤 자동차용 LNT, SCR 촉매의 배출가스 흡착, 탈리 및 열화 특성)

  • Seo, C.K;Kim, H.N.;Choi, B.C.
    • Journal of Power System Engineering
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    • v.14 no.6
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    • pp.13-19
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    • 2010
  • 이 논문에서는 디젤자동차용 LNT와 SCR 촉매의 NO, $NH_3$ 흡착 및 탈리의 기본 특성과 수열화 온도와 시간 및 정량화된 황피독 농도에 대한 de-$NO_x$ 촉매의 내구성을 평가하였다. LNT 촉매는 열적으로 열화됨에 따라 Pt 및 Ba의 소결 및 응집으로 활성이 떨어져 $NO_x$ 전환율은 감소하였다. 반면에 Pt의 비활성화로 중간생성물인 $NH_3$ 생성량은 증가하였으며, 이때 생성된 $NH_3$는 LNT+SCR 복합시스템의 SCR 촉매의 환원제 역할을 담당한다. 1.0 g/L 이상의 황이 피독된 LNT 촉매는 탈황을 하여도 질소 산화물 흡장물질(Ba) 의 성능이 회복이 되지 않아 $NO_x$ 전환율은 회복되지 않았으며, 탈황 후 Pt 재활성화로 인해 NO2 및 SCR 환원제인 $NH_3$ 생성량은 증가하였다. SCR 촉매의 $NO_x$ 전환율은 $700^{\circ}C$ 36h, $800^{\circ}C$ 24h로 수열화 시킨 촉매는 전이금속 입자 성장 및 zeolite 구조 파괴로 인하여 급격하게 떨어졌으며, 0.36 g/L 황 피독된 촉매는 zeolite가 가지는 강산성 특정으로 내피독성이 강하여 탈황시 $NO_x$ 전환율은 회복되었다.

Evaluation of possibility using cobalt poly-pyrrole carbon as an alternative oxygen reduction catalyst in microbial fuel cells (미생물 연료전지 내 Cobalt poly-pyrrole carbon의 산소환원촉매로서의 평가)

  • Kwon, Jae-Hyeong;Joo, Jin-Chul;Ahn, Chang-Hyuk;Song, Ho-Myeon;Ahn, Ho-Sang
    • 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.

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Redox Behavior of Chromium Oxide-Zirconia Catalyst (산화크롬-질코니아 촉매의 산화-환원거동)

  • Sohn, Jong-Rack;Ryu, Sam-Gon
    • Applied Chemistry for Engineering
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    • v.3 no.4
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    • pp.663-669
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    • 1992
  • Chromium oxide/zirconia catalysts were prepared by dry impregnation of $Zr(OH)_4$ powder with aqueous solution of $(NH_4)_2CrO_4$ followed by calcining in air. The redox behavior of prepared catalysts were investigated by reacting cumene as test material over catalysts. As a result it was found that $Cr^{6+}$ species(as chromate) on the surface of catalyst was responsible for the formation of strong acid site and the catalytic activity for the dealkylation of cumene. However, much of the $Cr^{6+}$ species was reduced to $Cr^{3+}$ species by $H_2$ formed during the catalytic reaction of cumene and the reduced $Cr^{3+}$ species was an active site for dehydrogenation of cumene to form ${\alpha}$-methyl styrene. The reduced $Cr^{3+}$ species was also reoxidized to a $Cr^{6+}$ species after treatment with $O_2$ and consequently the deoxidized catalyst exhibited catalytic activity for the dealkylation reaction of cumene.

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STM Studies of Keggin-type and Wells-Dawson-type Heteropolyacid Catalysts (Keggin 형 및 Wells-Dawson 형 헤테로폴리산 촉매의 STM 연구)

  • Park, Gyo Ik;Barteau, Mark A.;Jung, Ji Chul;Song, In Kyu
    • Korean Chemical Engineering Research
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    • v.47 no.2
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    • pp.163-168
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    • 2009
  • Negative differential resistance(NDR) behaviors of Keggin-type and Wells-Dawson-type heteropolyacids with cation, heteroatom, and polyatom substitutions were investigated by scanning tunneling microscopy. A reliable correlation between NDR peak voltage and reduction potential of heteropolyacid catalysts was established. It was found that more reducible heteropolyacid catalyst showed NDR behavior at less negative voltage, regardless of the structural difference. Thus, NDR peak voltage of heteropolyacid catalyst could be utilized as a single correlating parameter for the reduction potential of heteropolyacid catalyst.

Effect of Containing Promoter on SCR Catalysts (SCR 촉매에 포함된 조촉매 영향)

  • Seo, Choong-Kil
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.9
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    • pp.474-481
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    • 2018
  • The policy-making and technological development of eco-friendly automobiles designed to increase their supply is ongoing, but the internal combustion engine still accounts for approximately 95% of automobiles in use. To meet the stricter emission regulations of internal combustion engines based on fossil fuels, the proportion of after-treatments for vehicles and (ocean going) vessels is increasing continuously. As diesel engines have high power and good fuel economy in addition to less CO2 emissions, their market share is increasing not only in commercial vehicles, but also in passenger cars. Because of the characteristics of the diesel combustion, however, NOx is generated in localized high-temperature combustion regions, and particulates are formed in the zones of diffusion combustion. LNT and urea-SCR catalysts have been developed for the after-treatment of exhaust gas to reduce NOx in diesel vehicles. This study examined the effect of a containing promoter on SCR catalysts to cope with the severe exhaust gas regulation. The de-NOx performance of the Mn-SCR catalyst was the best, and the de-NOx performance was improved as the ion exchange rate between Mn ion and Zeolyst was good and the activation energy was low. The de-NOx performance of the 7Cu-15Ba/78Zeoyst catalyst was 32% at $200^{\circ}C$ and 30% at $500^{\circ}C$, and showed the highest performance. The NOx storage material of BaO loaded as a promoter was well dispersed in the Cu-SCR catalyst and the additional de-NOx performance of BaO was affected by the reduction reaction of the Cu-SCR catalyst. Among the three catalysts, the 7Cu-15Ba/Zeolyst SCR catalyst was resistant to thermal degradation. The same type of CuO due to thermal degradation migrates and agglomerates because BaO reduces the agglomeration of the main catalyst CuO particles.

Decomposition of Methanol-Water on $M^{II}$/ Cu / ZnO system ($M^{II}$/ Cu / ZnO 계에서의 메탄올-물의 반응)

  • Young-Sook Lee;Chong-Soo Han;Min-Soo Cho;Kae-Soo Rhee
    • Journal of the Korean Chemical Society
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    • v.32 no.1
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    • pp.22-29
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    • 1988
  • The reaction of methanol-water mixture to $CO_2$ and $H_2$ on alkaline earth metal-copper-zinc oxide has been studied in the temperature range of 150 ${\sim}\;300^{\circ}C$. Generally the addition of the alkaline earth metal to Cu/ZnO resulted in an enhancement of selectivity for $CO_2$ formation and a reduction of catalytic activity. Measurable activities were found from 150$^{\circ}C$, 200$^{\circ}C$, and 250$^{\circ}C$ on Mg/Cu/ZnO, Ca/Cu/ZnO, and Ba/Cu/ZnO respectively. However, the highest selectivity for $CO_2$ formation was observed in Ba/Cu/ZnO catalyst at 250$^{\circ}C$. The effect of alkaline earth metal or ZnO on the reactivity was investigated using temperature programmed desorption of $CO_2$ or temperature programmed reduction with $H_2$ over catalysts respectively. It was found that $CO_2$ interacts more strongly in the sequence of MgO < CaO < BaO and ZnO decereases the reduction temperature of CuO. From the results, it was suggested that ZnO activates $H_2$ in the redox process of Cu component and alkaline earth metals adsorbs $CO_2$ in the catalytic process.

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Activity and Characteristics of Cu-Mn Oxide Catalysts Supported on γ-Al2O3 (γ-Al2O3에 담지된 Cu-Mn 산화물 촉매의 활성 및 특성)

  • Kim, Hye-jin;Choi, Sung-Woo;Lee, Chang-Seop
    • Korean Chemical Engineering Research
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    • v.44 no.2
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    • pp.193-199
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    • 2006
  • The catalytic oxidation of toluene over $-Al_2O_3$ supported copper-manganese oxide catalysts in the temperature range of $160-280^{\circ}C$ was investigated by employing a fixed bed flow reactor. The catalysts were characterized by BET, scanning electron microscopy (SEM), temperature-programmed reduction(TPR), temperature-programmed oxidation(TPO), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction(XRD) techniques. Catalytic oxidation of toluene was achieved at the below $280^{\circ}C$, and the optimal content of copper and manganese in the catalyst was found to be 15.0 wt%Cu-10.0 wt%Mn. From the TPR/TPO and XPS results, the redox peak of 15 Cu-10 Mn catalyst shifted to the lower temperature, and the binding energy was shifted to the higher binding energy. Furthermore, It is considered that $Cu_{1.5}Mn_{1.5}O_4$ is superior to Mn oxides and CuO in the role as active factor of catalysts from the XRD results and also catalytic activities are dependent on the redox ability and high oxidation state of catalysts.