• Corrosion Science and Technology
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• 제21권5호
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• pp.412-417
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• 2022

Proton exchange membrane fuel cells (PEMFCs) provide zero emission power sources for electric vehicles and portable electronic devices. Although significant progresses for the widespread application of electrochemical energy technology have been achieved, some drawbacks such as catalytic activity, durability, and high cost of catalysts still remain. Pt-based catalysts are regarded as the most efficient catalysts for sluggish kinetics of oxygen reduction reaction (ORR). However, their prohibitive cost limits the commercialization of PEMFCs. Therefore, we proposed a NiCo@Au core shell structure as Pt-free ORR electrocatalyst in PEMFCs. NiCo alloy was synthesized as core to introduce ionization tendency and autoxidation reaction. Au as a shell was synthesized to prevent oxidation of core NiCo and increase catalytic activity for ORR. Herein, we report the synthesis, characterization, electrochemical properties, and PEMFCs performance of the novel NiCo@Au core-shell as a catalyst for ORR in PEMFCs application. Based on results of this study, possible mechanism for catalytic of autoxidation core@anti-oxidation shell in PEMFCs is suggested.

• 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.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.839-844
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• 2014

The gas-phase radical-radical reaction $O(^3P)$ + $C_2H_5$ (ethyl) ${\rightarrow}$ $H(^2S)$ + $CH_3CHO$(acetaldehyde) was investigated by applying a combination of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration and ab initio calculations. The two radical reactants $O(^3P)$ and $C_2H_5$ were respectively produced by photolysis of $NO_2$ and supersonic flash pyrolysis of the synthesized precursor azoethane. Doppler profile analysis of the nascent H-atom products in the Lyman-${\alpha}$ region revealed that the average translational energy of the products and the average fraction of the total available energy released as translational energy were $5.01{\pm}0.72kcalmol^{-1}$ and 6.1%, respectively. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title exchange reaction is a major channel and proceeds via an addition-elimination mechanism through the formation of a short-lived, dynamical addition complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed small kinetic energy release can be explained in terms of the loose transition state with a product-like geometry and a small reverse activation barrier along the reaction coordinate.

• Bulletin of the Korean Chemical Society
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• 제18권9호
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• pp.972-976
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• 1997

Single phase ruthenium oxides with perovskite (ATi1-xRuxO3 (A=Ca, Sr)) and pyrochlore structure (Bi2Ru2O7, Pb2Ru2O6.5) have been prepared reproducibly by solid state reaction methods and their electrocatalytic activities for oxygen evolution have been examined by Tafel plots. Tafel slopes vary from a low value of 42 mV/decade up to 222 mV/decade at room temperature. The high exchange current densities and high Tafel slopes compared with those obtained from the RuO2 DSA electrode at the crystalline single phase metal oxide electrodes suggest that they are better electrocatalysts at low overpotentials. A favorable change in the Tafel slope for the oxygen evolution reaction occurs as the ruthenium content increases. Substitution of Ti for Ru in the perovskite solid solutions enhanced their chemical stability by losing marginal electrochemical activity.

• 한국재료학회지
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• 제28권11호
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• pp.633-639
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• 2018

In anion exchange membrane fuel cells, Pd nanoparticles are extensively studied as promising non-Pt catalysts due to their electronic structure similar to Pt. In this study, to fabricate Pd nanoparticles well dispersed on carbon support materials, we propose a synthetic strategy using mixed organic ligands with different chemical structures and functions. Simultaneously to control the Pd particle size and dispersion, a ligand mixture composed of oleylamine(OA) and trioctylphosphine(TOP) is utilized during thermal decomposition of Pd precursors. In the ligand mixture, OA serves mainly as a reducing agent rather than a stabilizer since TOP, which has a bulky structure, more strongly interacts with the Pd metal surface as a stabilizer compared to OA. The specific roles of OA and TOP in the Pd nanoparticle synthesis are studied according to the mixture composition, and the oxygen reduction reaction(ORR) activity and durability of highly-dispersed Pd nanocatalysts with different particles sizes are investigated. The results of this study confirm that the Pd nanocatalyst with large particles has high durability compared to the nanocatalyst with small Pd nanoparticles during the accelerated degradation tests although they initially indicated similar ORR performance.

• Bulletin of the Korean Chemical Society
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• 제16권1호
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• pp.21-26
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• 1995

Electrochemical reduction of oxygen has been carried out at glassy carbon electrode and carbon ultramicroelectrode, the surface of which is modified with a new Co(Ⅱ)-Schiff base complex, Co(Ⅱ)-3,4-bis(salicylidene diimine)toluene in 1 M KOH solution. The results obtained from cyclic voltammetric and chronoamperometric experiments are consistent with the formation of the reasonably stable superoxide ions as a primary electron transfer reaction product. The exchange rate constant obtained for oxygen reduction is about 0.02 cm/s.

• 한국표면공학회지
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• 제51권5호
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• pp.332-336
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• 2018

Alkaline oxygen electrocatalysis, targeting anion exchange membrane alkaline-based metal-air batteries has become a subject of intensive investigation because of its advantages compared to its acidic counterparts in reaction kinetics and materials stability. However, significant breakthroughs in the design and synthesis of efficient oxygen reduction catalysts from earth-abundant elements instead of precious metals in alkaline media still remain in high demand. One of the most inexpensive alternatives is carbonaceous materials, which have attracted extensive attention either as catalyst supports or as metal-free cathode catalysts for oxygen reduction. Also, carbon composite materials have been recognized as the most promising because of their reasonable balance between catalytic activity, durability, and cost. In particular, heteroatom (e.g., N, B, S or P) doping on carbon materials can tune the electronic and geometric properties of carbon, providing more active sites and enhancing the interaction between carbon structure and active sites. Here, we focused on boron and nitrogen doped nanocarbon composit (BNC nanocarbon) catalysts synthesized by a solution plasma process using the simple precursor of pyridine and boric acid without further annealing process. Additionally, guidance for rational design and synthesis of alkaline ORR catalysts with improved activity is also presented.

• 공업화학
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• 제16권1호
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• pp.123-130
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• 2005

산소 PSA용 흡착제의 제조를 위하여 표면적이 큰 제올라이트 X형 흡착제를 합성하고 양이온교환을 통하여 질소의 선택적 흡착 능력이 우수한 흡착제로 제조하였다. 제올라이트 X형 흡착제는 50 L급 대형 반응기에서 $SiO_2\;:\;Na_2O\;:\;H_2O\;:\;Al_2O_3$ = 2.5 : 3.5 : 150 : 1의 조성으로 $98^{\circ}C$, 18 h 동안 반응한 결과 표면적이 $650m^2/g$ 이상의 표면적을 나타내었다. 흡착제의 양이온교환은 Li, Ag, Ca, Br, Sr 등의 금속 이온을 대상으로 조사하였다. Ag 이온의 이온교환 속도가 가장 빠르게 일어났으며 모든 금속 이온이 제올라이트 X형에 포함된 Na 이온과 거의 당량적으로 이온 교환이 일어남을 알 수 있었다. 양이온 교환된 제올라이트 X형 흡착제의 질소와 산소의 흡착 성능을 $10{\sim}40^{\circ}C$, 0~9 atm의 범위에서 측정한 결과 이온교환을 하지 않은 NaX 흡착제에 비하여 월등히 높은 흡착 성능을 나타내었으며 이온 교환된 제올라이트 X형 흡착제의 질소 흡착량은 0.5 atm 이하의 저압에서는 Ag > Li > Ca > Sr > Ba > K 이온의 순으로 나타났으나 1 atm 이상의 고압에서는 Li > Ag > Ca > Sr > Ba > K 이온의 순으로 나타났다. 공기의 조성에 준하는 질소 및 산소의 분압에서 흡착량의 비를 조사하여 질소/산소 분리도를 측정한 결과 $20^{\circ}C$의 온도에서 Li으로 이온 교환된 흡착제의 분리도는 13.023을 나타내었다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 추계학술대회
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• pp.368-371
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• 2006

[ $La_{0.8}Sr_{0.2}Co_{1-x}Mn_xO_3$ ] cathode as a high performance cathode on YSZ electrolyte was studied by analyzing impedance spectra. It was shown that cathode property of $La_{0.8}Sr_{0.2}Co_{1-x}Mn_xO_3$ is bet ter than that of$La_{0.8}Sr_{0.2}CoO_3$. At $700^{\circ}C$ in air environment, $La_{0.8}Sr_{0.2}Co_{0.4}Mn_{0.6}O_3$ cathode on CGO- layered YSZ electrolyte showed very low area specific resistance of $0.14{\Omega}cm^2$, which is low enough for intermediate-temperature sol id oxide fuel cells. This is because material properties of ionic conductivity and thermal expansion compatibility with electrolyte were optimized. Judging from activation energy and oxygen part i al pressure dependance of cathode property, it was noted that oxygen surface exchange kinetics is dominantly influential on cathode property in higher temperature region than $700^{\circ}C$ and oxygen self-diffusion in cathode material is more influential in lower temperature region.

• Bulletin of the Korean Chemical Society
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• 제19권6호
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• pp.661-666
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• 1998

Active reaction sites and electrochemical O2 reduction kinetics on La_{1-x}Sr_xMnO_{3+{\delta}} (x=0.1-0.4)/YSZ (yttria-stabilized zirconia) electrodes are investigated in the temperature range of 700-900 ℃ at $Po_2=10^{-3}$-0.21 atm. Results of the steady-state polarization measurements, which are formulated into the Butler-Volmer formalism to extract transfer coefficient values, lead us to conclude that the two-electron charge transfer step to atomically adsorbed oxygen is rate-limiting. The same conclusion is drawn from the $Po_2$-dependent ac impedance measurements, where the exponent m in the relationship of $I_o$ (exchange current density) ∝ $P_{o_{2}}^m$ is analyzed. Chemical analysis is performed on the quenched Mn perovskites to estimate their oxygen stoichiometry factors (δ) at the operating temperature (700-900 ℃). Here, the observed δ turns out to become smaller as both the Sr-doping contents (x) and the measured temperature increase. A comparison between the 8 values and cathodic activity of Mn perovskites reveals that the cathodic transfer coefficients $({\alpha}_c)$ for oxygen reduction reaction are inversely proportional to δ whereas the anodic ones $({\alpha}_a)$ show the opposite trend, reflecting that the surface oxygen vacancies on Mn perovskites actively participate in the $O_2$ reduction reaction. Among the samples of x= 0.1-0.4, the manganite with x=0.4 exhibits the smallest 8 value (even negative), and consistently this electrode shows the highest ${\alpha}_c$ and the best cathodic activity for the oxygen reduction reaction.