• Journal of the Korean Chemical Society
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• v.38 no.11
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• pp.785-791
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• 1994

The $Sr_1-_xY_xMnO_3$ (x = 0.0∼1.0) system was synthesized using amorphous citrate process. The stability of various structures and the electronic transport properties of this system were investigated. X-ray diffraction study indicated that the $Sr_1-_xY_xMnO_3$ system has three different structures depending on composition, namely, 4L-hexagonal perovskite (when x is less than 0.3), pseudocubic perovskite (when x is 0.3∼0.7), and hexagonal nonperovskite (when x is larger than 0.7) structures. The structural changes and electronic properties were interpreted based on two factors, i.e., the size of cations and the oxidation state of manganese ion. When the concentration of Y substitution exceeds 30%, the Mn-Mn repulsive interaction dominates over intermetallic attraction, and thus structure changes to pseudocubic perovskite. In perovskite phase the unit cell dimensions increases with increasing $Mn^{3+}$ ions due to yttrium substitution. The band gap of $Sr_{0.9}Y_{0.1}MnO_3$ is greater than that of $Sr_{0.5}Y_{0.5}MnO_3$. The greater band gap of $Sr_{0.9}Y_{0.1}MnO_3$ indicates that the 4L-hexagonal structure is more stabilized than cubic perovskite due to the Mn-Mn bond.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1310-1314
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• 2006

Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

• Journal of the Mineralogical Society of Korea
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• v.5 no.1
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• pp.1-5
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• 1992

The manganese oxide ores in the Taebaeg Mt. region have been formed by supergene weathering of the primary hydrothermal or sedimentary manganese ores. The supergenesis is controlled by the physical chemistry of the descending groundwater in the supergene zone. It includes the fundamental geological processes, such as dissolution, oxidation, transportation, precipitation, and crystallization and recrystallization. However, the fundamental mechanisms for the formation of various manganese oxide minerals are 1) replacement, 2) precipitation from solution, and 3) solid state crystallization and recrystallization. Various textures and structures of ores have been formed by these processes. Detailed paragenetic sequence of manganese oxide minerals in each ore deposit is summerized.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.511-516
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• 2004

A Li$[Co_{0.17}Li_{0.28}Mn_{0.55}]O_2$ cathode compound was prepared by a simple combustion method. The X-ray diffraction pattern showed that this compound could be classified as ${\alpha} -NaFeO_2$ structure type with the lattice constants of a = 2.8405(9) ${\AA}$ and c = 14.228(4) ${\AA}$. According to XANES analysis, the oxidation state of Mn and Co ions in the compound were 4+ and 3+, respectively. During the first charge process, the irreversible voltage plateau at around 4.65 V was observed. The similar voltage-plateau was observed in the initial charge profile of other solid solution series between $Li_2MnO_3\;and\;LiMnO_2$ (M=Ni, Cr...). The first discharge capacity was 187 mAh/g and the second discharge capacity increased to 204 mAh/g. As the increase of cycling number, one smooth discharge profile was converted to two distinct sub-plateaus and the discharge capacity was slowly decreased. From the Co and Mn K-edge XANES spectra measured at different cyclic process, it can be concluded that irreversible transformation of phase is occurred during continuous cycling process.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.91-91
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• 2013

Imagine a world where we could biomanufacture hybrid nanomaterials having atomic-scale resolution over functionality and architecture. Toward this vision, a fundamental challenge in materials science is how to design and synthesize protein-like material that can be fully self-assembled and exhibit information-specific process. In an ongoing effort to extend the fundamental understanding of protein structure to non-natural systems, we have designed a class of short peptides to fold like proteins and assemble into defined nanostructures. In this talk, I will talk about new strategies to drive the self-assembled structures designing sequence of peptide. I will also discuss about the specific interaction between proteins and inorganics that can be used for the development of new hybrid solar energy devices. Splitting water into hydrogen and oxygen is one of the promising pathways for solar to energy convertsion and storage system. The oxygen evolution reaction (OER) has been regarded as a major bottleneck in the overall water splitting process due to the slow transfer rate of four electrons and the high activation energy barrier for O-O bond formation. In nature, there is a water oxidation complex (WOC) in photosystem II (PSII) comprised of the earthabundant elements Mn and Ca. The WOC in photosystem II, in the form of a cubical CaMn4O5 cluster, efficiently catalyzes water oxidation under neutral conditions with extremely low overpotential (~160 mV) and a high TOF number. The cluster is stabilized by a surrounding redox-active peptide ligand, and undergo successive changes in oxidation state by PCET (proton-coupled electron transfer) reaction with the peptide ligand. It is fundamental challenge to achieve a level of structural complexity and functionality that rivals that seen in the cubane Mn4CaO5 cluster and surrounding peptide in nature. In this presentation, I will present a new strategy to mimic the natural photosystem. The approach is based on the atomically defined assembly based on the short redox-active peptide sequences. Additionally, I will show a newly identified manganese based compound that is very close to manganese clusters in photosystem II.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.1
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• pp.1-8
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• 2017

Cu/Mn/Ce catalysts for water gas shift (WGS) reaction were synthesized by urea-nitrate combustion method with the fixed molar ratio of Cu/Mn as 1:4 and 1:1 with the doping concentration of Ce from 0.3 to 0.8 mol%. The prepared catalysts were characterized with SEM, BET, XRD, XPS, $H_2$-TPR, $CO_2$ TPD, $N_2O$ chemisorption analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The Cu/Mn(CM) catalysts formed Cu-Mn mixed oxide of spinel structure ($Cu_{1.5}Mn_{1.5}O_4$) and manganese oxides ($MnO_x$). However, when a small amount of Ce was doped, the growth of $Cu_{1.5}Mn_{1.5}O_4$ was inhibited and the degree of Cu dispersion were increased. Also, the doping of Ce on the CM catalyst reduced the reduction temperature and the base site to induce the active site of the catalyst to be exposed on the catalyst surface. From the XPS analysis, it was confirmed that maintaining the oxidation state of Cu appropriately was a main factor in the WGS reaction. Consequently, Ce as support and dopant in the water gas shift reaction catalysts exhibited the enhanced catalytic activities on CM catalysts. We found that proper amount of Ce by preparing catalysts with different Cu/Mn ratios.

• Korean Chemical Engineering Research
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• v.52 no.4
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• pp.443-450
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• 2014

Selective catalytic reduction of nitrogen monoxide by hydrogen ($H_2$-SCR of NO) over platinum catalysts impregnated on zirconia-incorporated silica ($ZrO_2-SiO_2$) and manganese oxide ($MnO_x$) was investigated. $Pt-MnO_x$ catalyst showed low conversions and low yields of $N_2O$ and $NO_2$ at $100{\sim}350^{\circ}C$. On the other hand, NO conversions over $Pt/ZrO_2-SiO_2$ were very high, but $N_2O$ was predominantly produced at $100-150^{\circ}C$ and the yield of $NO_2$ increased with temperature at $200-300^{\circ}C$, resulting in poor $N_2$ yields. $Pt-MnO_x/ZrO_2-SiO_2$ exhibited a small enhancement in $N_2$ yield at $100-150^{\circ}C$ due to the synergy of $MnO_x$ and $ZrO_2-SiO_2$. The surface composition and oxidation state of the catalyst components and the acidity of the catalysts were examined. IR spectra of the adsorption of NO and their subsequent reactions with hydrogen on these catalysts were also recorded. The variations of conversion and product yield according to the catalyst components in the $H_2$-SCR of NO were discussed in relation to their catalytic roles.

• Journal of Electrochemical Science and Technology
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• v.2 no.1
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• pp.1-7
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• 2011

Nanocomposites of reduced graphene oxide and manganese (II,III) oxide can be synthesized by the freeze-drying process of the mixed colloidal suspension of graphene oxide and manganese oxide, and the subsequent heat-treatment. The calcined reduced graphene oxide-manganese (II,III) oxide nanocomposites are X-ray amorphous, suggesting the formation of homogeneous and disordered mixture without any phase separation. The reduction of graphene oxide to reduced graphene oxide upon the heat-treatment is evidenced by Fourier-transformed infrared spectroscopy. Field emission-scanning electronic microscopy and energy dispersive spectrometry clearly demonstrate the formation of porous structure by the house-of-cards type stacking of reduced graphene oxide nanosheets and the homogeneous distribution of manganese ions in the nanocomposites. According to Mn K-edge X-ray absorption spectroscopy, manganese ions in the calcined nanocomposites are stabilized in octahedral symmetry with mixed Mn oxidation state of Mn(II)/Mn(III). The present reduced graphene oxide-manganese oxide nanocomposites show characteristic pseudocapacitance behavior superior to the pristine manganese oxide, suggesting their applicability as electrode material for supercapacitors.

• Journal of the Korean Ceramic Society
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• v.39 no.6
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• pp.523-527
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• 2002

LiMn$_2$O$_4$ compounds were synthesized by calcining a mixture of LiOH and MnO$_2$(CMD) at 47$0^{\circ}C$ for 10 h and then calcining again at $650^{\circ}C$ to 90$0^{\circ}C$ fur 48 h in air with intermediate grinding. All the synthesized samples exhibited XRD patterns for the cubic spinel phase with a space group Fd3m. The lattice parameter increased gradually as the sintering temperature rose. The electrochemical cells were charged and discharged fur 20 cycles at a current density 300$\mu$A/$\textrm{cm}^2$ between 3.5 V and 4.3 V. The voltage vs. discharge capacity curves for all the samples showed two plateaus. The LiMn$_2$O$_4$ sample calcined at 90$0^{\circ}C$ had the largest first discharge capacity. This sample exhibited the best crystallinity, had relatively large lattice parameter and had relatively large particles with rectatively homogeneous size. All the samples showed good cycling performances. Among all the samples, the LiMn$_2$O$_4$ calcined at 85$0^{\circ}C$ had relatively large first discharge capacity and very good cycling performance. The addition of excess LiOH and the mixing in ethanol considered to help the formation of the more LiMn$_2$O$_4$ phase per unit weight sample and the more stable LiMn$_2$O$_4$phase. These led to the larger discharge capacities and the better cycling performances. The cyclic voltammograms fur the second cycle of the LiMn$_2$O$_4$ samples showed the oxidation and reduction peaks around 4.05 V and 4.18 V and around 4.08 V and 3.94 V, respectively. The larger first discharge capacity of the sample calcined at the higher temperature is related to the larger lattice parameter.

• Journal of the Mineralogical Society of Korea
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• v.30 no.1
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• pp.21-29
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• 2017

Surface soils on Barton Peninsula, King George Island, West Antarctica were investigated to acquire the mineralogical and geochemical data of soil in Antarctica. Multiline of techniques for example, X-ray diffraction (XRD), transmission electron microscopy (TEM)-electron energy loss spectroscopy (EELS), and wet chemistry analysis were performed to measure the composition of clay minerals, Fe-oxidation states, cation exchange capacity, and total cation concentration. Various minerals in sediments such as smectite, illite, chlorite, kaolinite, quartz and plagioclase were identified by XRD. Fe-oxidation states of bulk soils showed 20-40% of Fe(II) which would be ascribed to the reduction of Fe in clays as well as Fe-bearing minerals. Moreover, redox states of Fe in smectite structure was a ~57% of Fe(III) consistent to the values for the bulk soils. The cation exchange capacity of bulk soils ranged from 100 to 300 meq/kg and differences were not significantly measured for the sampling locations. Total cations (Mg, K, Na, Al, Fe) of bulk soils varies, contrast to the heavy metals (Co, Ni, Cu, Zn, Mn). These results suggested that composition of bed rocks influenced the distribution of elements in soil environments and soils containing clay compositions may went through the bio/geochemical alteration.