• Bulletin of the Korean Chemical Society
• /
• v.24 no.6
• /
• pp.864-880
• /
• 2003

A unified picture for magnetism, superconductivity, quantum optics and other properties of molecule-based materials has been presented on the basis of effective model Hamiltonians, where necessary parameter values have been determined by the first principle calculations of cluster models and/or band models. These properties of the matetials are qualitatively discussed on the basis of the spin and pseudo-spin Hamiltonian models, where several quantum operators are expressed by spin variables under the two level approximation. As an example, ab initio broken-symmetry DFT calculations are performed for cyclic magnetic ring constructed of 34 hydrogen atoms in order to obtain effective exchange integrals in the spin Hamiltonian model. The natural orbital analysis of the DFT solution was performed to obtain symmetry-adapted molecular orbitals and their occupation numbers. Several chemical indices such as information entropy and unpaired electron density were calculated on the basis of the occupation numbers to elucidate the spin and pair correlations, and bonding characteristic (kinetic correlation) of this mesoscopic magnetic ring. Both classical and quantum effects for spin alignments and singlet spin-pair formations are discussed on the basis of the true spin Hamiltonian model in detail. Quantum effects are also discussed in the case of superconductivity, atom optics and quantum optics based on the pseudo spin Hamiltonian models. The coherent and squeezed states of spins, atoms and quantum field are discussed to obtain a unified picture for correlation, coherence and decoherence in future materials. Implications of theoretical results are examined in relation to recent experiments on molecule-based materials and molecular design of future molecular soft materials in the intersection area between molecular and biomolecular materials.

• Korean Journal of Environmental Agriculture
• /
• v.29 no.3
• /
• pp.273-281
• /
• 2010

Concentration of antibiotics including a tetracycline group (TCs) of tetracycline (TC), chlortetracycline (CTC), and oxytetracycline (OTC), a sulfonamide group (SAs) of sulfamethoxazole (SMX), sulfathiazole (STZ), and sulfamethazine (SMT), an ionophore group (IPs) of lasalocid (LSL), monensin (MNS), and salinomycin (SLM), and a macrolide group (MLs) of tylosin (TYL) was determined from samples collected from the agricultural soil, stream water, and sediment. For the agricultural soil samples, the concentration of TCs had the highest value among all tested antibiotic's groups due to its high accumulation rate on the surface soils. The lower concentrations of SAs in the agricultural soils may be resulted from its lower usage and lower distribution coefficient (Kd) compared to TCs. The concentration of TCs in stream water was significantly increased through June to September. It would be likely due to soil loss during an intensive rainfall event and a reduction of water level after the monsoon season. A significant amount of TCs in the sediment was also detected due to its accumulation from runoff, which occurred by complexation of divalent cations, ion exchange, and hydrogen bonding among humic acid molecules. To ensure environmental or human safety, continuous monitoring of antibiotics residues in surrounding ecosystems and systematic approach to the occurrence mechanism of antibiotic resistant bacteria are required.

• Membrane Journal
• /
• v.15 no.3
• /
• pp.247-254
• /
• 2005

Chitosan film has potential applications in agriculture, food, and pharmacy. However, films made only from chitosan lack gas barrier and have poor mechanical properties. For enhanced gas barrier and mechanical properties, chitosan/clay nanocomposites have been prepared with montmorillonite (MMT) which is a layered structure of clays and chitosan. The cationic biopolymer, chitosan is intercalated into $Na^+-montmorillonite$ through cationic exchange and hydrogen bonding process. Diluted acetic acid is used as solvent f3r dissolving and dispersing chitosan. Chitosan was intercalated or exfoliated in MMT and it was confirmed by X-ray diffraction method. D-spacing of the characteristic peak from MMT plate in chitosan/clay nanocomposites was moved and diminished. The thermal stability and the mechanical properties of the nanocomposites are measured by TGA and Universal Testing Machine. Gas permeability through the chitosan/clay nanocomposites films decreased due to increased tortuosity made by intercalation of clay in chitosan.

• Membrane Journal
• /
• v.21 no.1
• /
• pp.30-38
• /
• 2011

Composite membranes based on sulfonated poly(aryl ether) sulfone (SPAES) with different sulfated zirconia nanoparticles ($s-ZrO_2$) ratio are synthesized and investigated for the improvement of the hydration and the proton conductivity at high temperature and no humidification for fuel cell applications. X-ray diffraction technique is employed to characterize the structure and the size of $s-ZrO_2$ nanoparticles. The sulfation effect of $s-ZrO_2$ nanoparticles is verified by FT-IR analysis. The properties of the SPAES composite membranes with the various $s-ZrO_2$ ratio are evaluated by ion exchange capacity and water content. The proton conductivities of the composite membranes are estimated at room temperature with full hydration and at the various high temperature without external humidification. The composite membrane with 5 wt% $s-ZrO_2$ shows the highest proton conductivity. The proton conductivities are $0.9292\;S\;cm^{-1}$ at room temperature with full hydration and $0.0018\;S\;cm^{-1}$ at $120^{\circ}C$ without external humidification, respectively.

• Resources Recycling
• /
• v.27 no.6
• /
• pp.53-58
• /
• 2018

Solvent extraction of Li(I) from weak HCl solution was investigated by the mixture of TBP/MIBK with other neutral extractants such as Cyanex 923, TOPO and TOP. The TBP/MIBK organic phase was loaded with 0.1 M $FeCl_3$ at different HCl concentrations (1-9 M). Extraction of Li(I) from weak HCl solution is related to the stability of $FeCl_3$ in the organic mixture. As HCl concentration increased in preparing the loaded TBP phase, the stripping percentage of Fe(III) during the extraction of Li(I) became reduced and thus Li(I) could be extracted by ion exchange reaction with hydrogen ion in the organic. The concentration of TBP in the extractant mixture affected the stability of $FeCl_3$. Compared to TBP, Fe(III) was easily stripped from the loaded MIBK and thus no Li(I) was extracted by the mixture with MIBK. The nature of neutral extractant with TBP/MIBK showed little difference in the extraction of Li(I) and stripping of Fe(III).

• Korean Chemical Engineering Research
• /
• v.57 no.3
• /
• pp.344-350
• /
• 2019

Durability is very important for the commercialization of membranes and electrode assemblies (MEA) developed for proton exchange membrane fuel cells (PEMFC). Durability evaluation of stationary PEMFC MEA has a problem that the voltage change rate should be measured for a long time over 1000 hours under constant current conditions. In this study, the electrochemical durability evaluation protocol of membranes (OCV holding method) using to vehicle MEAs was applied to the stationary MEA for the purpose of shortening the durability evaluation time. After operation of the stationary and automobile MEA for 168 hours under conditions of OCV, cathode oxygen, $90^{\circ}C$ and relative humidity of 30%, I-V, LSV, CV, impedance and FER were measured and compared. When the hydrogen permeability, OCV change, ionic conductivity, and fluorine flow rate, which represent the durability of the membrane after degradation, were all examined, it was shown that durability of stationary MEA membrane was better than that of vehicles MEA membrane. In addition, the electrode degradation of stationary MEA was smaller than that of vehicles MEA after degradation operation. It was possible to evaluate in a short time using automotive protocol that the durability of stationary MEA was superior that of vehicle MEA in terms of membrane and the electrode.

• 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.