• Korean Chemical Engineering Research
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• 제44권4호
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• pp.356-362
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• 2006

본 연구에서는 석탄가스화복합발전(integrated gas combined cycle, 이하 IGCC) 시스템의 석탄가스화기로부터 생산되는 석탄가스가 환원제로 이용되는 $SO_2$ 환원공정인 직접 황 회수 공정(direct sulfur recovery process, 이하 DSRP)에서 이용 가능한 Sn-Zr계 촉매 상에서의 $SO_2$ 환원반응특성을 조사하였다. Sn-Zr계 촉매는 0/1, 1/4, 1/1, 2/1, 3/1, 1/0의 Sn/Zr 몰비로 조절하여 침전법 및 공침법으로 제조되었다. 공간속도가 $10,000ml/g_{-cat.}{\cdot}h$, 반응물 몰비$([CO(or\;H_2)]/[SO_2])$가 2.0인 반응조건 하에서 Sn-Zr계 촉매를 이용하여 온도를 변화시킨 가운데 석탄가스에 포함되어 있는 $H_2$ 또는 CO를 환원제로 사용하여 $SO_2$ 환원에 대한 반응특성이 조사되었다. 실험 결과, 환원제의 종류에 상관없이 $SnO_2$와 $ZrO_2$보다 Sn-Zr계 촉매가 활성이 더 높았으며, 환원제의 종류에 대한 반응성 조사 결과, $H_2$보다 CO가 $SO_2$ 환원에 더 높은 반응성을 나타내었다. $H_2$가 환원제로 이용된 $SO_2$ 환원특성을 조사한 결과, Sn/Zr 비에 따라 제조된 Sn-Zr계 촉매의 종류에 상관없이 온도가 증가함에 따라 반응성이 증가하는 경향을 보이며 Sn/Zr 몰비가 1/4인 촉매를 사용한 경우 $550^{\circ}C$에서 $SO_2$전환율이 94.4％, 원소 황 수율이 66.4％로 높은 반응성을 나타내었다. 반면 CO를 환원제로 이용한 경우에는 Sn/Zr 몰비가 높은 촉매일수록 최적 반응온도가 감소되는 특이한 경향을 나타내었다. Sn-Zr계 촉매 중 Sn/Zr 몰비가 3/1인 $SnO_2-ZrO_2$ 촉매가 가장 낮은 최적 반응온도에서 높은 반응성을 나타내었는데, $325^{\circ}C$에서 $SO_2$전환율이 약 100％, 원소 황 수율이 약 99.5％로 가장 높은 반응성을 얻었다. 그리고 CO가 $H_2$보다 더 많이 포함되어 있는 석탄모사가스에 대하여 환원제로서의 이용가능성을 확인하고자 $CO/H_2$ 비를 달리한 각각의 합성가스에 대하여 $SO_2$ 환원반응실험을 수행하였다. Sn/Zr 몰비가 2/1인 Sn-Zr계 촉매 상에서 $SO_2$ 환원반응 실험 결과, CO 함량이 높은 합성가스일수록 효과적인 환원제임을 확인할 수 있었다. 따라서 Sn-Zr계 촉매가 적용된 DSRP에서 석탄모사가스가 환원제로 이용 가능하다는 것을 알 수 있었다.

• 한국분말재료학회지
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• 제18권3호
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• pp.244-249
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• 2011

Spherical nanosized cobalt powder with an average size of 150-400 nm was successfully prepared at room temperature from cobalt sulfate heptahydrate ($CoSO_4{\cdot}7H_2O$). Wet chemical reduction method was adopted to synthesize nano cobalt powder and hypophosphorous acid ($H_3PO_2$) was used as reduction agent. Both the HCP and the FCC Co phase were developed while $CoSO_4{\cdot}7H_2O$ concentration ranged from 0.7 M to 1.1 M. Secondary phase such as $Co(OH)_2$ and $CO_3O_4$ were also observed. Peaks for the crystalline Co phase having HCP and FCC structure crystallized as increasing the concentration of $H_3PO_2$, indicating that the amount of reduction agent was enough to reduce $Co(OH)_2$. Consequently, a homogeneous Co phase could be developed without second phase when the $H_3PO_2/CoSO_4{\cdot}7H_2O$ ratio exceeded 7.

• 한국세라믹학회지
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• 제35권12호
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• pp.1336-1336
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• 1998

2단계 열탄소환원법으로 탄화규소 휘스커를 Ar과 H2분위기에서 기상-고상, 2단계, 기상-액상-고상 성장기구를 통해 각각 합성하였다. Ar분위기에서 탄화규소 휘스커는 다음과 같은 반응기구로 성장하였다. SiO2(S)+C(s)-SiO(v)+CO(v) SiO(v)3CO(v)=SiC(s)whisker+2CO2(v) 2C(s)+2CO2(v)=4CO(v) 이때 전체 반응속도는 세번째 반응에 참여하는 탄소에 의해 지배되었다. 따라서 이 반응이 휘스커 합성의 율속반응으로 판단되었다. 한편 H2 분위기에서 탄화규소 휘스커는 다음과 같은 반응기구로 성장하였다.SiO2(s)+C(s)=SiO(v)+CO(v) 2C(s)+4H2(v)=2CH4(v) SiO(v)+2CH4(v)=SiC(s)whisker+CO(v)+4H2(v) 이때 전체 반응속도는 SiO(v) 기체의발생 속도에 의해 지배되었다. 따라서 첫번째 반응이 휘스커 합성의 율속 반응인 것으로 판단되었다.

• 분석과학
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• 제11권6호
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• pp.460-468
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• 1998

$SOPDH_2$, $SNDH_2$, $EBNH_2$, $PBNH_2$ Schiff base 리간드와 이들의 [$Co(II)(SND)(H_2O)_2$], [$Co(II)(SOPD)(H_2O)_2$], [$Co(II)(EBN)(H_2O)$], [$Co(II)(PBN)(H_2O)$] 착물들을 합성하였다. Co(II) 착물들에서 Schiff base 리간드와 Co(II)의 몰 결합 비는 1:1로 주어졌으며 6배위 결합을 합성하였다. Co(II) 착물이 수식된 유리질 탄소전극을 사용하여 1 M KOH 수용액에서 산소 환원 반응을 순환 전압전류법으로 알아보았다. Schiff base Co(II) 착물이 수식된 전극에서의 산소의 환원 전류는 알몸 유리질 탄소전극에서 보다 더 증가하였고 환원 전위는 양전위 방향으로 더 이동하였다. 산소 환원 반응에 관여한 전자수와 교환 속도 상수 값은 순환 전압전류 곡선으로부터 구하였다. 산소 환원 반응경로는 최종 생성물이 $H_2O_2$로 가는 $2e^-$ 전이 반응을 나타내었으며 촉매가 수식된 전극에서의 교환 속도 상수는 알몸전극의 값에 비해 약 2~10배 정도 증가하였다.

• Bulletin of the Korean Chemical Society
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• 제19권8호
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• pp.825-830
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• 1998

The electrocatalytic reduction of dioxygen by Co(TTFP)(Y)2 {Y=H2O or HO-} is investigated by cyclic voltammetry, spectroelectrochemistry, hydrodynamic voltammetry at a glassy carbon electrode in dioxygen-saturated aqueous solutions. Electrocatalytic reduction of dioxygen by CoⅡ(TTFP)(Y)2 establishes a pathway of 2e- reduction to form hydrogen peroxide, and then the generated hydrogen peroxide is reduced to water by CoⅠ(TTFP)(Y)2 at more negative potential. CoⅡ(TTFP)(Y)2 may bind dioxygen to produce the adduct complex [CoⅡ-O2 or CoⅢ-O2] which exhibits a Soret band at 411 nm and Q band at 531 nm.

• 한국연소학회지
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• 제20권3호
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• pp.8-12
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• 2015

The CO reduction characteristics of hot air stream diluted with exhaust gas in a perfectly stirred reactor (PSR) were investigated numerically. The dilution ratio ($\Omega$), inlet temperature ($T_{in}$), and residence time ($\tau$) were considered as parameters to investigate the effects of those on the emission indices for CO and $CO_2$ (EICO and $EICO_2$). The roles of dominant reactions and the production rates of major species were analyzed. It was found from the EICO trend that the supplied CO in the air stream was consumed. The EICO increased negatively with $T_{in}$ at fixed $\tau$ regardless of $\Omega$. However, the magnitude of EICO and minimum inlet temperature for CO reduction showed complicated trend according to the variation of $\tau$. It was identified that the OH radical, generated from the reactions, $O_2+H{\leftrightarrow}O+OH$ and $2OH{\leftrightarrow}H+H_2O$, affected the CO reduction by the reaction, $CO+OH{\leftrightarrow}H+CO_2$. However, the CO emission ratio increased at sufficiently high inlet temperature range due to the thermal dissociation of $CO_2$.

• Journal of Electrochemical Science and Technology
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• 제13권4호
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• pp.462-471
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• 2022

In this study, the electrochemical impedance characteristics of CO₂/H₂O co-reduction to produce CO/H₂ syngas were investigated in a low-temperature single cell. The effect of the operating conditions on the single-cell performance was evaluated at different feed concentrations and cell voltages, and the corresponding electrochemical impedance spectroscopy (EIS) data were collected and analyzed. The Nyquist plots exhibited two semicircles with separated characteristic frequencies of approximately 1 kHz and tens of Hz. The high-frequency semicircles, which depend only on the catholyte concentration, could be correlated to the charge transfer processes in competitive CO₂ reduction and hydrogen evolution reactions at the cathodes. The EIS characteristics of the CO₂/H₂O co-reduction single cell could be explained by the equivalent circuit suggested in this study. In this circuit, the cathodic mass transfer and anodic charge transfer processes are collectively represented by a parallel combination of resistance and a constant phase element to show low-frequency semicircles. Through nonlinear fitting using the equivalent circuit, the parameters for each electrochemical element, such as polarization resistances for high- and low-frequency processes, could be quantified as functions of feed concentration and cell voltage.

• Bulletin of the Korean Chemical Society
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• 제19권4호
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• pp.417-422
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• 1998

The electrocatalytic reduction of molecular oxygen was investigated with a Co(II)-glyoxal bis(2-hydroxyanil) complex coated-glassy carbon (GC) electrode in aqueous media. The reduction of $O_2$ at the modified electrode was an irreversible and diffusion-controlled reaction. The complex coated-GC electrode demonstrated an excellent electrocatalytic effect for $O_2$ reduction in an acetate buffer solution of pH 3.2. The coated electrode made the $O_2$ reduction potential shift of 60-510 mV in a positive direction compared to the bare GC electrode depending on pH. The Co(II)-glyoxal bis(2-hydroxyanil) coated electrode converted about 51% of the $O_2$ to $H_2O_2$ via a two-electron reduction pathway, with the balance converted to H_2O$.

• Journal of Electrochemical Science and Technology
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• 제7권2호
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• pp.91-96
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• 2016

Oxidation behaviours of ash free coal (AFC), carbon, and H₂ fuels were investigated with a coin type molten carbonate fuel cell. Because AFC has no electrical conductivity, its oxidation occurs via gasification to H₂ and CO. An interesting behaviour of mass transfer resistance reduction at higher current density was observed. Since the anode reaction has the positive reaction order of H₂, CO₂ and H₂O, the lack of CO₂ and H₂O from AFC results in a significant mass transfer resistance. However, the anode products of CO₂ and H₂O at higher current densities raise their partial pressure and mitigate the resistance. The addition of CO₂ to AFC reduced the resistance sufficiently, thus the resistance reduction at higher current densities did not appear. Electrochemical impedance results also indicate that the addition of CO₂ reduces mass transfer resistance. Carbon and H₂ fuels without CO₂ and H₂O also show similar behaviour to AFC: mass transfer resistance is diminished by raising current density and adding CO₂.

• 한국전기전자재료학회논문지
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• 제35권3호
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• pp.308-310
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• 2022

Ultrawide bandgap gallium oxide (Ga₂O₃) semiconductors are known to have excellent photocatalytic properties due to their high redox potential. In this study, CO₂ reduction is demonstrated using nanostructured Ga₂O₃ photocatalyst under ultraviolet (254 nm) light source conditions. After the CO₂ reduction, C₂H₄ remained as a by-product in this work. Nanostructured Ga₂O₃ photocatalyst also showed an excellent endurance characteristic. Photogenerated electron-hole pairs boosted the CO₂ reduction to C₂H₄ via nanostructured Ga₂O₃ photocatalyst, which is attributed to the ultrawide and almost direct bandgap characteristics of the gallium oxide semiconductor. The findings in this work could expedite the realization of CO₂ reduction and a simultaneous C₂H₄ production using a low cost and high performance photocatalyst.