• Bulletin of the Korean Chemical Society
• /
• v.22 no.2
• /
• pp.164-170
• /
• 2001

The crystal structures of fully dehydrated Ni2+- and Tl+ -exchanged zeolite X (Ni17Tl58-X, and Ni12Tl68-X; X=Si100Al92O384) have been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd3 at $21(1)^{\circ}C$ (a=24.380(4) $\AA$, 24.660(4) $\AA$, respectively). Their structures have been refined to the final error indices R1=0.037 and R2=0.043 with 485 reflections, and R1=0.039 and R2=0.040 with 306 reflections, respectively, for which I >36(I). In Ni17Tl58-X, 17 Ni2+ ions per unit cell were found at only two sites: 15 at site I at the center of the hexagonal prism (Ni-O=2.203(9) $\AA)$ and the remaining 2 at site II near single six-oxygen rings in the supercage (Ni-O=2.16(3) $\AA).$ Fifty-eight Tl+ ions were found at five crystallographic sites: 28 at site II (Tl-O=2.626(8) $\AA)$, 2 at site I' in the sodalite cavity near the hexagonal prism (Tl-O=2.85(1) $\AA)$, another 2 at site II' in the sodalite cavity (Tl-O=2.77(1) $\AA).$ The remaining 26 were found at two nonequivalent Ⅲ' sites with occupancies of 23 and 3. In Ni12Tl68-X, 12 Ni2+ ions per unit cell were found at two sites: 10 at site I (Ni-O=2.37(2) $\AA)$ and the remaining 2 at site II (Ni-O=2.13(2) $\AA).$ Sixty-eight Tl+ ions were found at five crystallographic sites: 28 at site II (Tl-O=2.63(1) $\AA)$, 12 at site I' (Tl-O=2.62(1) $\AA)$, 2 at site II' (Tl-O=3.01(2) $\AA)$, and the remaining 26 at two III' sites with occupancies of 23 and 3. It appears that Ni 2+ ions prefer to occupy site I and II, in that order. The large Tl+ ions occupy the remaining sites, I', II, II' and two different III' sites. In both crystals, only the Ni2+ ions at site II were reduced and migrated to the external surface of zeolite X when these crystals were treated with hydrogen gas.

• Korean Chemical Engineering Research
• /
• v.60 no.2
• /
• pp.202-207
• /
• 2022

The study on electrode degradation of Proton Exchange Membrane Fuel Cell (PEMFC) was mainly studied on the particle growth and active area reduction of Pt on the electrode. The degradation of the electrode catalyst Pt in contact with the membrane affects the deterioration of the polymer membrane, but there are not many studies related to this. In this study, the phenomenon of the deposition of deteriorated Pt inside the polymer membrane during the accelerated electrode catalyst degradation test and its effects were studied. The voltage change (0.6 V ↔ 0.9 V) was repeated up to 30,000 cycles to accelerate the platinum degradation rate. When the voltage change cycle was repeated while oxygen was introduced into the cathode, the amount of Pt deposited inside the film was larger than when nitrogen was introduced. As the number of voltage change cycles increased, the amount of Pt deposited inside the membrane increased, and Pt dissolved in the cathode moved toward the anode, showing a uniform distribution throughout the membrane at 20,000 cycles. In the process of the accelerated electrode catalyst degradation test, the hydrogen crossover current density of the membrane did not change, and it was confirmed that the deposited Pt did not affect the durability of the membrane.

• Korean Chemical Engineering Research
• /
• v.61 no.2
• /
• pp.189-195
• /
• 2023

As a PEMFC (Polymer Exchange Membrane Fuel Cell) cathode catalyst, Pt-Co/C has recently been widely used because of its improved durability. In a fuel cell, electrodes and electrolytes have a close influence on each other in terms of performance and durability. The effect on the electrochemical durability of the electrolyte membrane when Pt-Co/C was replaced in the Pt/C electrode catalyst was studied. The durability of Pt-Co/C MEA (Membrane Electrode Assembly) was higher than that of Pt/C MEA in the electrochemical accelerated degradation process of PEMFC membrane. As a result of analyzing the FER (Fluorine Emission Rate) and hydrogen permeability, it was shown that the degradation rate of the membrane of Pt-Co/C MEA was lower than that of Pt/C MEA. In the OCV (Open Circuit Voltage) holding process, the rate of decrease of the active area of the Pt-Co/C electrode was lower than that of the Pt/C electrode, and the amount of Pt deposited on the membrane was smaller in Pt-Co/C MEA than in Pt/C MEA. Pt inside the polymer membrane deteriorates the membrane by generating radicals, so the degradation rate of the membrane of Pt/C MEA with a high Pt deposition rate was higher than Pt-Co/C MEA. When the Pt-Co/C catalyst was used, the electrode durability was improved, and the amount of Pt deposited on the membrane was also reduced, thereby improving the electrochemical durability of the membrane.

• Korean Chemical Engineering Research
• /
• v.61 no.3
• /
• pp.356-361
• /
• 2023

In order to improve the durability of the proton exchange membrane fuel cell (PEMFC), it is important to accurately evaluate the durability of the polymer membrane in a short time. The test conditions for chemically accelerated durability evaluation of membranes are high voltage, high temperature, low humidity, and high gas pressure. It can be said that the protocol is developed by changing these conditions. However, the relative influence of each test condition on the degradation of the membrane has not been studied. In chemical accelerated degradation experiment of the membrane, the influence of 4 factors (conditions) was examined through the factor experiment method. The degree of degradation of the membrane after accelerated degradation was determined by measuring the hydrogen permeability and effluent fluoride ion concentration, and it was possible to determine the degradation order of the polymer membrane under 8 conditions by the difference in fluoride ion concentration. It was shown that the influence of the membrane degradation factor was in the order of voltage > temperature > oxygen pressure > humidity. It was confirmed that the degradation of the electrode catalyst had an effect on the chemical degradation of the membrane.

• Korean Chemical Engineering Research
• /
• v.61 no.4
• /
• pp.517-522
• /
• 2023

A chemical/mechanical durability test of polymer membrane evaluation method is used in which air and hydrogen are supplied to the proton exchange membrane fuel cell (PEMFC) and wet/dry is repeated in the open circuit voltage (OCV) state. In this protocol, when wet/dry is repeated, voltage increase/decrease is repeated, resulting in electrode degradation. When the membrane durability is excellent, the number of voltage changes increases and the evaluation is terminated due to electrode degradation, which may cause a problem that the original purpose of membrane durability evaluation cannot be performed. In this study, the same protocol as the department of energy (DOE) was used, but oxygen was used instead of air as the cathode gas, and the wet/dry time and flow rate were also increased to increase the chemical/mechanical degradation rate of the membrane, thereby shortening the durability evaluation time of the membrane to improve these problems. The durability test of the Nafion 211 membrane electrode assembly (MEA) was completed after 2,300 cycles by increasing the acceleration by 2.6 times using oxygen instead of air. This protocol also accelerated degradation of the membrane and accelerated degradation of the electrode catalyst, which also had the advantage of simultaneously evaluating the durability of the membrane and the electrode.

• Economic and Environmental Geology
• /
• v.42 no.6
• /
• pp.575-589
• /
• 2009

Groundwater has been extracted for irrigation in Sacheon-Hadong area, which is close to the South Sea. We analyzed chemical components of groundwater to examine the effects of seawater intrusion and agricultural activities in the study area. Most groundwater samples displayed the Na/Cl concentration ratios similar to that of seawater (0.55) with an increasing tendency of electrical conductivity ($227-7,910\;{\mu}S/cm$) towards the coast. In addition, statistical interpretation of the cumulative frequency curves of Cl and $HCO_3$ showed that 30.1% of the groundwater samples were highly affected by seawater intrusion. Groundwaters in the study area mostly belonged to the Ca-Cl and Na-Cl type, demonstrating that they were highly influenced by seawater intrusion and cation exchange. The result of oxygen-hydrogen isotope analysis demonstrated slightly higher $\delta^{18}O$ ((-8.53)-(-6.13)‰) and ${\delta}D$ ((-58.7)-(-43.7)‰) comparing to mean oxygen-hydrogen isotope ratios in Korea. As a result of nitrogen isotope analysis, the $\delta^{15}N-NO_3$ values ((-0.5)-(19.1)‰) indicate two major sources of nitrate pollution (organic nitrogen in soil and animal and human wastes) and mixed source of the two. However, denitrification may partly contribute as a source of nitrogen. According to factor analysis, four factors were identified among which factor 1 with an eigenvalue of 6.21 reflected the influence of seawater intrusion. Cluster analysis indicated the classification of groundwater into fresh, saline, and mixed ones.

• Clean Technology
• /
• v.13 no.1 s.36
• /
• pp.54-63
• /
• 2007

Even traces of CO in the hydrogen-rich feed gas to proton exchange membrane fuel cells (PEMFC) poison the platinum anode electrode and dramatically decrease the power output. In this work, a variety of catalytic materials consisting of $Cu/Ce_xZr_{1-x}O_2$, (x = 0.0-1.0) were synthesised, characterized and tested for CO oxidation and preferential oxidation of CO (PROX). These catalysts prepared by hydrothermal and deposition-precipitation methods. The catalysts were characterized by XRD, XRF, SEM, BET, $N_2O$ titration and oxygen storage capacity (OSC) measurement. The effects of composition of the support and degree of excess oxygen were investigated fur activity and $CO_2$ selectivity with different temperatures. The composition of the support markedly influenced the PROX activity. Among the various $Cu/Ce_xZr_{1-x}O_2$ catalysts having different composition, $Cu/Ce_{0.9}Zr_{0.1}O_2$ and $Cu/Ce_{0.7}Zr_{0.3}O_2$ showed the highest activities (>99%) and selectivities (ca.50%) in the temperature range of $150{\sim}160^{\circ}C$. It was found that by using of $Ce_xZr_{1-x}O_2$ mixed oxide support which possesses a high oxygen storage capacity, oxidation-reduction activity of Cu-based catalyst was improved, which resulted in the increase of catalytic activity and selectivity of CO oxidation in excess $H_2$ environments.

• Journal of the Korean Electrochemical Society
• /
• v.10 no.1
• /
• pp.25-30
• /
• 2007

Proton exchange membrane fuel cell(PEMFC) performance could be affected by various factors such as cell temperature, total pressure, partial pressure of reactants and relative humidity. Hydrogen ion is combined with water to form hydronium ion [$H_3O^+$] and pass through membrane resulting electricity generation. Cooling system is needed to remove heat and other uses on large scale fuel cell. In case that collant conductivity is increased, fuel cell performance could be decreased because produced electricity could be leaked through coolant. In this study, triple distilled water(TDW) and antifreeze solution containing ethylene glycol was used to observe resistance change. Resistance of TDW was taken 28 days to reach preset value, and effect on fuel cell operation was not observed. Resistance of antifreeze solution was not reached to preset value up to 48 days, but performance failure occurred presumably caused by bipolar plate junction resulting stoppage resistance experiment. Generally PEMFC humidification is performed near-saturated operating conditions at various temperatures and pressures, but non-humidifying condition could be applied in small scale fuel cell to improve efficiency and reduce system cost. However, it was difficult to operate large scale fuel cell without humidifying, especially higher than $50{\sim}60^{\circ}C$. In case of small flux such as 0.78 L/min, temperature difference between inlet and outlet was occurred larger than other cases resulting performance decrease. Non-humidifying performance experiments were done at various cell temperature. When both of anode and cathode humidification were removed, cell performance was strongly depended on cell operating temperature.

• Journal of Korean Society of Environmental Engineers
• /
• v.28 no.7
• /
• pp.704-712
• /
• 2006

This research was designed to investigate the removal of heavy metals, such as $Al^{3+}$, $Cu^{2+}$, $Mn^{2+}$, $Pb^{2+}$ and $Zn^{2+}$, by adsorption on clay minerals. Bentonite(Raw-Bentonite), $Ca^{2+}$ and $Na^+$ ion exchanged bentonite(Ca- and Na-Bentonite) and montmorillonite, such as KSF and K10 from Sigma Aldrich, were used as adsorbents. The component of five inorganic adsorbents was analyzed by XRF, and the concentration of metal ions was measured by ICP. The cation exchange capacity(CEC) and the particle charge of adsorbents were measured. The initial concentration range of metal ions was $10{\sim}100$ mg/L. From the experimental results, it was shown that the adsorption equilibrium was attained after $1{\sim}2$ hours. The maximum percentage removal of $Al^{3+}$, $Cu^{2+}$, $Pb^{2+}$ and $Zn^{2+}$ on Na-Bentonite were more than 98% and that of $Mn^{2+}$ was 66%. $Al^{3+}$ was leached out from KSF with the higher concentration of hydrogen ion. Percentage removals of $Pb^{2+}$ and $Zn^{2+}$ on KSF were 88% and 59%, respectively. In general, the percentage removal of metal ions was decreased with the higher initial concentration of metal ions. The adsorption capacity of metal ions on Na-Bentonite was $1.3{\sim}19$ mg/g. Freundlich equation was used to fit the acquired experimental data. As the results, the adsorption capacity of metal ions was in the order of Na-Bentonite$\gg$Raw-Bentonite$\cong$K10>Ca-Bentonite>KSF. Freundlich constant, K of Na-Bentonite was the largest for metal ions. The order K of Na-Bentonite was Al>Cu>Pb>Zn>Mn, and the adsorption intensity(1/n) was determined to be $0.2{\sim}0.39$.

• Journal of the Society of Cosmetic Scientists of Korea
• /
• v.49 no.1
• /
• pp.87-96
• /
• 2023

This study was conducted to discover substances that regulate skin surface acidification using human epidermal keratinocyte cell lines, and to investigate their effects on the moisturizing ability and skin barrier function of the stratum corneum. Prunella vulgaris (P. vulgaris) is an herb widely distributed in Northwest Africa and North America that has been studied for its anti-apoptotic, antioxidant, and anti-inflammatory effects. However, research on the regulation of NHE1 expression and the restoration of skin barrier function has not been conducted. Analysis of P. vulgaris revealed the presence of rosmarinic acid and caffeic acid as active ingredients, which were tested for toxicity in human epidermal keratinocyte cell lines (HaCaT), and showed no toxic effects were observed at high concentarion (100 ㎍/mL or 100 µM). It is known that sodium-hydrogen ion exchange pumps (NHE1) decrease in expression in aging skin to maintain the acidic pH of the stratum corneum, and it is hypothesized that this decrease plays an important role in the impaired restoration of skin barrier function in aging skin. P. vulgaris extract and caffeic acid increased the expression of NHE1 in keratinocytes, increased the expression of natural moisturizing factor (NMF) precursor filaggrin and ceramide synthesis enzyme serine palmitoyl transferase (SPT). In addition, P. vulgaris and caffeic acid decreased the extracellular pH of keratinocytes, indicating a direct effect on skin pH regulation. Taken together, these results suggest that P. vulgaris and caffeic acid can regulate skin pH through NHE1 modulation, and may help to restore skin barrier function by increasing NMF and ceramide synthesis. These results show the possibility that honeysuckle and caffeic acid can have a positive effect on skin health, and can be the basis for the development of new skin protection products using them.