• Korean Journal of Materials Research
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• v.33 no.2
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• pp.29-46
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• 2023

The electrochemical reduction of carbon dioxide (CO₂) to value-added products is a remarkable approach for mitigating CO₂ emissions caused by the excessive consumption of fossil fuels. However, achieving the electrocatalytic reduction of CO₂ still faces some bottlenecks, including the large overpotential, undesirable selectivity, and slow electron transfer kinetics. Various electrocatalysts including metals, metals oxides, alloys, and single-atom catalysts have been widely researched to suppress HER performance, reduce overpotential and enhance the selectivity of CO₂RR over the last few decades. Among them, single-atom catalysts (SACs) have attracted a great deal of interest because of their advantages over traditional electrocatalysts such as maximized atomic utilization, tunable coordination environments and unique electronic structures. Herein, we discuss the mechanisms involved in the electroreduction of CO₂ to carbon monoxide (CO) and the fundamental concepts related to electrocatalysis. Then, we present an overview of recent advances in the design of high-performance noble and non-noble singleatom catalysts for the CO₂ reduction reaction.

• Analytical Science and Technology
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• v.9 no.2
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• pp.161-167
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• 1996

An investigation was made of possible ways in which one could control the relative rates of cadmium deposition and hydrogen evolution by binary additive systems. Benzyl alcohol was employed as an additives due to its ability to form a hydrophobic film which inhibit the electroreduction of water to form hydrogen. The second additive was chosen to make the cadmium(II) ion less hydrophilic and increase its ability to cross the hydrophobic benzyl alcohol film and be electrodeposited at the cathode. It was shown by voltammetric and current efficiency studies that ion pairing and complexing additives could be used to accelerate the reduction of cadmium in the presence of the benzyl alcohol film. It was also shown that the benzyl alcohol film lowered the dielectric constant of the solution near the electrode enough to obtain ion pairing between the sodium ion and the negative chloride complex of cadmium and accelerate the reduction of the cadmium. This acceleration did not occur in the sulfate solution in the absence of chloride since cadmium(II) is primarily present as a positive aquo complex and ion pairing, if it occured, would not accelerate but would hinder reduction of cadmium.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1806-1808
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• 2014

We report the successful preparation of gold nanoparticles (Au NPs) using a novel electroreduction process, which is simple, fast, and environmentally friendly (toxic chemicals such as strong reducing agents are not required). Our process allows for the mass production of Au NPs and adequate particle size control. The Au NPs prepared show high biocompatibility and are non-toxic to healthy human cells. By applying radio-frequency (RF) ablation, we monitored the electro-hyperthermia effect of the Au NPs at different RFs. The Au NPs exhibit a fast increase in temperature to $55^{\circ}C$ within 5 min during the application of an RF of 13 MHz. This temperature rise is sufficient to promote apoptosis through thermal stress. Our work suggests that the selective Au NP-mediated electro-hyperthermia therapy for tumor cells under an RF of 13 MHz has great potential as a clinical treatment for specific tumor ablation.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3835-3839
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• 2013

A new synthesis route for Pt nanoparticles by direct electrochemical reduction of a solid-state Pt ion precursor ($K_2PtCl_6$) is demonstrated. Solid $K_2PtCl_6$-supported polyethyleneimine (PEI) coatings on the surface of glassy carbon electrode were prepared by simple mixing of solid $K_2PtCl_6$ into a 1.0% PEI solution. The potential cycling or a constant potential in a PBS (pH 7.4) medium were applied to reduce the solid $K_2PtCl_6$ precursor. The reduction of Pt(IV) began at around -0.2 V and the reduction potential was ca. -0.4 V. A steady state current was achieved after 10 potential cycling scans, indicating that continuous formation of Pt nanoparticles by electrochemical reduction occurred for up to 10 cycles. After applying the reduction potential of -0.6 V for 300 s, Pt nanoparticles with diameters ranging from $0.02-0.5{\mu}m$ were observed, with an even distribution over the entire glassy carbon electrode surface. Characteristics of the Pt nanoparticles, including their performance in electrochemical reduction of $H_2O_2$ are examined. A distinct reduction peak observed at about -0.20 V was due to the electrocatalytic reduction of $H_2O_2$ by Pt nanoparticles. From the calibration plot, the linear range for $H_2O_2$ detection was 0.1-2.0 mM and the detection limit for $H_2O_2$ was found to be 0.05 mM.

• Analytical Science and Technology
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• v.8 no.4
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• pp.675-682
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• 1995

Thin films of buckminsterfullerene($C_{60}$) formed by solution drop casting on Pt foil electrode surfaces were studied by cyclic voltammetry(CV) in acetonitrile(MeCN) containing quaternary ammonium or alkali-metal salts as supporting electrolyte. The electrochemical behaviors of $C_{60}$ films are found to be strongly dependent on the nature of the supporting electrolytes, especially with tetrabutyl ammonium perchlorate (TBAP, $NBu_4ClO_4$), and tetrabutyl ammonium tetrafluoroborate ($TBABF_4$, $NBu_4BF_4$). Reasonably stable films are formed into which electrons can be injected. The interaction of $C_{60}$ film with the quaternary ammonium cation may produce the fulleride salts $(TBA^+)(C{_{60}}^-)$ and $(TBA^+)_2(C{_{60}}^{2-})$. The bulk electroreduction with a controlled potential to generate the soluble $C{_{60}}^{3-}$ anions(dark red-brown color) is followed by electrooxidative deposition to produce a neutral $C_{60}$ film on the surface. The peak currents($I_{pc}$ and $I_{pa}$) of these thin film were dramatically decreased with repetitive potential scanning. These results could be explained by the adsorption-desorption phenomena and ion pairing interaction of reduced species($C{_{60}}^-$, and $C{_{60}}^{2-}$) onto the electrode surface. The peak current changes and peak potential shifts of the thin $C_{60}$ film in cyclic voltammograms formed from solution were observed by varying scan rates.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2017.10a
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• pp.73-73
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• 2017

Pyroprocessing at KAERI (Korea Atomic Energy Research Institute) consists of pretreatment, electroreduction, electrorefining and electrowinning. SFR (Sodium Fast Reactor) fuel is prepared from the electrowinning process which is composed of LCC (Liquid Cadmium Process) and Cd distillation et al. LCC is an electrochemical process to obtain actinides from spent fuel. In order to recover actinides inert anodes such as carbon material are used, where chlorine gas ($Cl_2$) evolves on the surface of the carbon material. And, stainless steel (SUS) crucible should be installed in large-scale electrowinning system. Therefore, the effect of chlorine on the SUS material needs to be studied. LiCl-KCl-$UCl_3$-$NdCl_3$-$CeCl_3$-$LaCl_3$-$YCl_3$ salt was contained in 2 kinds of electrolytic crucible having an inner diameter of 5cm, made of an insulated alumina and an SUS, respectively. And, three kinds of electrodes such as cathode, anode, reference were used for the electrochemical experiments. Both solid tungsten (W) and LCC were used as cathodes. Cd of 45 g as the cathode material was contained in alumina crucibles for the deposition experiments, where the crucible has an inner diameter of 3 cm. Glassy carbon rod with the diameter of 0.3 cm was employed as an anode, where shroud was not used for the anode. A pyrex tube containing LiCl-KCl-1mol% AgCl and silver (Ag) wire having a diameter of 0.1cm was used as a reference electrode. Electrodeposition experiments were conducted at $500^{\circ}C$ at the current densities of $50{\sim}100mA/cm^2$. In conclusion, Fe ions were produced in the salt during the electrodeposition by the reaction of chlorine evolved from the anode and Fe of the SUS crucible and thereby LCC system using SUS crucible showed very low current efficiencies compared with the system using the insulated alumina crucible. Anode shroud needs to be installed around the glassy carbon not to influence surrounding SUS material.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.215-224
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• 1989

Electrochemical reductions of $trans-[Co(en)_2X_2](ClO_4)_n$ (where X is cyanide, nitrite, ammonia, and isothiocyanate) were investigated by cyclic voltammetry and polarography at mercury and glassy carbon electrode. $trans-[Co(en)_2(CN)_2]ClO_4$ was reduced to Co(II) complex followed by adsorption to the mercury electrode. Cyanide ion was not released from the reduced Co(II) complex but the cyanide and (en) were released after the reduction to metallic cobalt. The other complexes except $trans-[Co(en)_2(CN)_2]ClO_4$ were reduced to cobalt(II) complexes followed by release of monodendate ligand, and (en) was released at the reduction step to metallic cobalt. $trans-[Co(en)_2(NO_2)_2]ClO_4$ was reduced to cobalt(Ⅱ) complex, and $NO_2^-$ ion was released followed by electroreduction through ECE mechanism at pH 2. On glassy carbon electrode, all complexes of Co(III) were reduced to Co(II) complexes with irreversible one-electron diffusion controlled reaction in which (en) was not released at this step. Increasing absorption wave number of complexes caused to negative shift of peak potential.

• Journal of the Korean Chemical Society
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• v.37 no.5
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• pp.483-490
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• 1993

Voltammetric behavior of heavy lanthanide ions has been investigated by the DC, DPP and CV in acetonitrile solution. The reduction of $Gd^{3+}, Tb^{3+}, Dy^{3+}, Ho^{3+}, Er^{3+}, Tm^{3+} 및 Lu^{3+} proceed by three-electron change to the metallic state with totally irreversibility in 0.1M tetraethylammonium perchlorate. However, the reduction of Yb(Ⅲ) proceeds in two steps $(Yb^{3+} ＋ e^- \Leftrightarrow Yb^{2+} and Yb^{2+} ＋ 2e^- → Yb^0)$. The first reduction of Yb(Ⅲ) showed quasi reversible behavior, but the second reduction was irreversible in cyclic voltammetry. The cathodic peak current showed adsorptive properties in high concentration with lower sweep rate. The electroreduction of heavy lanthanides in water-acetonitrile mixture has been studied. In water-acetonitrile mixture, the negative shift of the peak potential and the decrease peak current were observed increasing water concentration. Also the Yb(Ⅲ) reduction to Yb(Ⅲ) has been deviated from quasi-reversible character with increase water amount. These results drive from the high solvation abilities of water which has high donor number.

• Korean Journal of Materials Research
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• v.30 no.4
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• pp.176-183
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• 2020

The high-temperature stability of YSZ specimens fabricated by die pressure and cold isostatic press (CIP) is investigated in CaCl₂-CaF₂-CaO molten salt at 1,150 ℃. The experimental results are as follows: green density 46.7 % and 50.9 %; sintering density 93.3 % and 99.3 % for die press and CIP, respectively. YSZ foremd by CIP exhibits higher stability than YSZ formed by die press due to denseness dependency after high-temperature stability test. YSZ shows peaks mainly attributed to CaZrO₃, with a small t-ZrO₂ peak, unlike the high-intensity tetragonal-ZrO₂ (t-ZrO₂) peak observed for the asreceived specimen. The t-ZrO₂ phase of YSZ is likely stabilized by Y₂O₃, and the leaching of Y₂O₃ results in phase transformation from t-ZrO₂ to m-ZrO₂. CaZrO₃ likely forms from the reaction between CaO and m-ZrO₂. As the exposure time increases, more CaZrO₃ is observed in the internal region of YSZ, which could be attributed to the inward diffusion of molten salt and outward diffusion of the stabilizer (Y₂O₃) through the pores. This results in greater susceptibility to phase transformation and CaZrO₃ formation. To use SOM anodes for the electroreduction of various metals, YSZ stability must be improved by adjusting the high-density in the forming process.

• Journal of Electrochemical Science and Technology
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• v.13 no.1
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• pp.148-158
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• 2022

The electrochemical CO₂ reduction (ECR) to produce value-added fuels and chemicals using clean energy sources (like solar and wind) is a promising technology to neutralize the carbon cycle and reproduce the fuels. Presently, the ECR has been the most attractive route to produce carbon-building blocks that have growing global production and high market demand. The electrochemical CO₂ reduction could be extensively implemented if it produces valuable products at those costs which are financially competitive with the present market prices. Herein, the electrochemical conversion of CO₂ obtained from flue gases of a power plant to produce diesel and formic acid using a consistent techno-economic approach is presented. The first scenario analyzed the production of diesel fuel which was formed through Fischer-Tropsch processing of CO (obtained through electroreduction of CO₂) and hydrogen, while in the second scenario, direct electrochemical CO₂ reduction to formic acid was considered. As per the base case assumptions extracted from the previous outstanding research studies, both processes weren't competitive with the existing fuel prices, indicating that high electrochemical (EC) cell capital cost was the main limiting component. The diesel fuel production was predicted as the best route for the cost-effective production of fuels under conceivable optimistic case assumptions, and the formic acid was found to be costly in terms of stored energy contents and has a facile production mechanism at those costs which are financially competitive with its bulk market price. In both processes, the liquid product cost was greatly affected by the parameters affecting the EC cell capital expenses, such as cost concerning the electrode area, faradaic efficiency, and current density.