• Bulletin of the Korean Chemical Society
• /
• v.19 no.9
• /
• pp.927-933
• /
• 1998

Polycrystalline powder of vanadium-doped forsterite (Vδ $Mg_2SiO_4$) was synthesized by the $H_2O_2$-assisted sol-gel method. The vanadium dopant, which was added as VO$(OMe)_3$ in methanol, went through several redox reactions as the sol-gel reaction proceeded. Upon adding VO$(OMe)_3$ to a mixture of $Mg(OMe)_2$ and Si$(OEt)_4$ in methanol, V(V) reduced to V(IV). As hydrolysis reaction proceeded, the V(IV) oxidized all back to V(V). Apparently, some of the V(V) reduced to V(IV) during subsequent gelation by condensation reaction. The V(IV) remained even after heat treatment of the gel in highly oxidizing atmosphere. The crystallization of the xerogel around 880 ℃ readily produced single phase forsterite without any minor phase. Using the polycrystalline powder as feeding stock, single crystals of vanadium-doped forsterite were grown by the floating zone method in oxidizing or reducing atmosphere. The doping was limited in low level because of the high partitioning of the vanadium in liquid phase during melting. The greenish single crystal absorbed visible light of 700∼1100 nm. But, no emission was obtained in near infrared range.

• Nuclear Engineering and Technology
• /
• v.54 no.2
• /
• pp.653-660
• /
• 2022

The interaction between UN and CdCl₂ in the LiCl-KCl molten eutectic was studied at 1023 K. The chlorination was monitored by sampling and recording the redox potential of the medium. At 1023 K the chlorination of UN with cadmium chloride in the molten LiCl-KCl eutectic proceeds completely and results in the formation of uranium chlorides. The melts of the LiCl-KCl-UCl₃ or LiCl-KCl-UCl₄ compositions can be obtained by the end of experiment depending on the presence of metallic cadmium in the reaction zone. The higher the concentration of the chlorinating agent, the faster the reaction rate. At [CdCl₂]/[UN] = 1.65 (10% excess) the reaction proceeds to completion in about 7.5 h. At [CdCl₂]/[UN] = 7 the complete chlorination takes 2.5-3 h.

• Korean Chemical Engineering Research
• /
• v.57 no.2
• /
• pp.239-243
• /
• 2019

In this study, anthraquinone-2,7-disulfonic acid (2,7-AQDS) is used as negative active material and Tiron is used as positive active material for aqueous redox flow battery (RFB). In previous results that used the 2,7-AQDS and Tiron, sulfuric acid ($H_2SO_4$) was a supporting electrolyte. However, in this study, ammonium chloride ($NH_4Cl$) is suggested as the electrolyte for the first time. By changing the supporting electrolyte from $H_2SO_4$ to $NH_4Cl$, the cell voltage of RFB is improved from 0.76 V to 1.01 V. To investigate the effect of $NH_4Cl$ supporting electrolyte of the performance of RFB, the full-cell tests of RFB using 2,7-AQDS and Tiron that are dissolved in $NH_4Cl$ supporting electrolyte are carried out, while cut-off voltage range is a main parameter to determine their performance. When the cut-off voltage range is 0.2~1.6 V, the hydrogen evolution occurs during charging step. To address the side reaction effect, the cut-off voltage range is changed to 0.2~1.2 V. When the revised cut-off voltage range is used and the current density of $40mA/cm^2$ is applied, hydrogen evolution is not observed and the optimal RFB shows the charge efficiency of 99% and discharge capacity of 3.3 Ah/L at 10cycle.

• Clean Technology
• /
• v.25 no.4
• /
• pp.296-301
• /
• 2019

This study was conducted to investigate the characteristics of CO oxidation by NO poisoning in Pt/TiO₂ catalyst prepared by wet impregnation method and calcined at 400 ℃. In order to confirm the NO poisoning effect of the Pt/TiO₂ catalyst, the change of reaction activity was observed when NO was injected during the CO+O₂ reaction where it was ascertained that the CO conversion rate rapidly decreased below 200 ℃. Also, CO conversion was not observed below 125 ℃. Recovery of initial CO conversion was not verified even if NO injection was blocked at 125 ℃. Accordingly, various analyses were performed according to NO injection. First, as a result of the TPD analysis, it was confirmed that NO pre-adsorption in catalyst inhibited CO adsorption and conversion desorption from adsorbed CO to CO₂. When NO was pre-adsorbed, it was confirmed through H₂-TPR analysis that the oxygen mobility of the catalyst was reduced. In addition, it was validated through FT-IR analysis that the redox cycle (Pt²⁺→Pt⁰→Pt²⁺) of the catalyst was inhibited. Therefore, the presence of NO in the Pt/TiO₂ catalyst was considered to be a poisoning factor in the CO oxidation reaction, and it was determined that the oxygen mobility of the catalyst is required to prevent NO poisoning.

• Transactions of the Korean hydrogen and new energy society
• /
• v.31 no.1
• /
• pp.57-64
• /
• 2020

The water-gas shift reaction for the compact reformer was carried out at a gas hourly space velocity of 72,152 h^-1 over the Cu-Nb-CeO₂ catalysts prepared by co-precipitation method. In order to investigate the effect of Nb₂O₅ promotion over a Cu-CeO₂ catalyst, the Nb₂O₅ loading amount was systematically changed from 0 to 5 wt.%. Among the prepared catalysts, the Cu-Nb-CeO₂ (1%) catalyst showed the highest catalytic activity (CO conversion=61% at 400℃) as well as 100% CO₂ selectivity. The high activity and stability of Cu-Nb-CeO₂ (1%) catalyst are correlated to high Brunauer-Emmett-Teller surface area, small metallic Cu crystallite size, and enhanced redox property.

• Applied Chemistry for Engineering
• /
• v.29 no.5
• /
• pp.541-548
• /
• 2018

In this work, the $N_2O$ decomposition catalyst and reaction characteristics to control the $N_2O$ removal were described. Experiments were carried out by using Rh as an active metal catalyst on various supports and the $Rh/CeO_2$ catalyst with $CeO_2$ support showed the best activity for the $N_2O$ decomposition when it was prepared under the constant heat treatment condition ($500^{\circ}C$-4 hr). $H_2-TPR$ and XPS analyzes were performed to confirm the effect of the physical and chemical properties of the catalyst on $N_2O$ decomposition. As a result, it was found that the increase of the oxygen transfer capacity of the catalyst due to the increase of both the redox property and $Ce^{3+}$ amount affected the decomposition reaction of $N_2O$. In addition, the future work will include a treatment process capable of decomposition $N_2O$ and NO under the condition that $N_2O$ and NO are simultaneously generated and its characteristics of $N_2O$ decomposition reaction.

• Journal of the Korean Chemical Society
• /
• v.32 no.3
• /
• pp.233-242
• /
• 1988

The uranium(VI) complexes with new unsaturated macrocyclic ligands of cryptand types and the neodymium(III) complexes with cryptand 222 and DBC ligands have been investigated polarographically in dimethylsulfoxide solvent. The reduction states, electron numbers involved in the reduction process, effects of the added acid on the polarograms of complexes, and the mechanisms of the reduction electrode reactions have been examined. The stability constants and mole-ratio of new complexes were also obtained by polarographic method. The reaction of ligands was controlled by the diffusion in the reduction with four electrons at a step, whereas the redox reaction with six electrons at three steps in $UO_2\;^{2+}$ complexes with macrocyclic ligands and the redox reaction with one electron at a step in $Nd^{3+}$ complexes with cryptand 222 and DBC have been observed. The imine ligands formed stable complexes with uranium(VI) above pH 7.0, and the neodymium(III) complexes with cryptand 222 and DBC ligands were stable above pH 4.0.

• Korean Chemical Engineering Research
• /
• v.43 no.2
• /
• pp.206-214
• /
• 2005

Heterogeneously-catalyzed oxidation of aqueous phase trichloroethylene (TCE) over supported metal oxides has been conducted to establish an approach to eliminate ppm levels of organic compounds in water. A continuous flow reactor system was designed to effect predominant reaction parameters in determining catalytic activity of the catalysts for wet TCE decomposition as a model reaction. 5 wt.% $CoO_x/TiO_2$ catalyst exhibited a transient period in activity vs. on-stream time behavior, suggesting that the surface structure of the $CoO_x$ might be altered with on-stream hours; regardless, it is probable to be the most promising catalyst. Not only could the bare support be inactive for the wet decomposition reaction at $36^{\circ}C$, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Very low TCE conversion appeared for $TiO_2$-supported $NiO_x$ and $CrO_x$ catalysts. Wet oxidation performance of supported Cu and Fe catalysts, obtained through an incipient wetness and ion exchange technique, was dependent primarily on the kinds of the metal oxides, in addition to the acidic solid supports and the preparation routes. 5 wt.% $FeO_x/TiO_2$ catalyst gave no activity in the oxidation reaction at $36^{\circ}C$, while 1.2 wt.% Fe-MFI was active for the wet decomposition depending on time on-stream. The noticeable difference in activity of the both catalysts suggests that the Fe oxidation states involved to catalytic redox cycle during the course of reaction play a significant role in catalyzing the wet decomposition as well as in maintaining the time on-stream activity. Based on the results of different $CoO_x$ loadings and reaction temperatures for the decomposition reaction at $36^{\circ}C$ with $CoO_x/TiO_2$, the catalyst possessed an optimal $CoO_x$ amount at which higher reaction temperatures facilitated the catalytic TCE conversion. Small amounts of the active ingredient could be dissolved by acidic leaching but such a process gave no appreciable activity loss of the $CoO_x$ catalyst.

• The Korean Journal of Ceramics
• /
• v.6 no.2
• /
• pp.177-182
• /
• 2000

At the porous $La_{0.6}Ca_{0.4}MnO_{3-{\delta}}$(LCM)/YSZ electrodes of solid oxide fuel cells (SOFC), the electrochemical redox reaction of oxygen proceeds via the triple boundary (TPB) of gas/LCM/YSZ. The surface diffusion of adsorbed oxygen on LCM has been proposed as the rate determining process, assuming the gradient of oxygen chemical potential from the outer surface of porous layer to TPB. Along with the formation of this gradient, oxygen nonstoichiometry in the bulk of LCM may varies. In this paper, an electrochemical technique was described precisely to determine the variation of oxygen content in LCM of porous LCM/YSZ under polarization. It was shown that the oxygen potential in LCM layer under large cathodic polarization is much lower than that in the gas phase, being determined from the electrode potential and Nernst equation.

• Nuclear Engineering and Technology
• /
• v.32 no.4
• /
• pp.309-315
• /
• 2000

The changes of Np oxidation state in nitric acid and the effect of nitrous acid on the oxidation state were analyzed by spectrophotometry, solvent extraction, and electrochemical methods. An enhancement of Np extraction to 30 vol.% TBP was carried out through adjustment of Np oxidation state by using a glassy carbon fiber column electrode system. The information of electrolytic behavior of nitric acid was important because the nitrous acid affecting the Np redox reaction was generated during the electrolytic adjustment of the Np oxidation state. The Np solution used in this work consisted of Np（V) and Np（Ⅵ）without （IV）. The composition of Np（V) in the range of 0.5M -5.5 M nitric acid was 32% ~ 19%. The electrolytic oxidation of Np（V) to Np（Ⅵ）in the solution enhanced Np extraction efficiency about five times higher than the case without the electrolytic oxidation. It was confirmed that the nitrous acid of less than about 10-5 M acted as a catalyst to accelerate the chemical oxidation reaction of Np（V) to Np（Ⅵ）.