• Journal of Korean Society of Environmental Engineers
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• v.33 no.4
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• pp.237-242
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• 2011

In this study, the catalytic activity of Mn-Phthalocyanine (Mn-PC) for VOCs (acetadehyde, propionaldehyde and toluene) combustion was determined. The reaction was carried out in a fixed bed reactor at the temperature range of $200{\sim}380^{\circ}C$. We investigated the physicochemical properties of Mn-PC before and after the pretreatment (air, $450^{\circ}C$, 1 hr, 60 cc/min) by TGA (Thermogravimetric Analyzer), BET (Brunauer Emmett Teller), EA (Elemental Analyzer), XRD (X-ray Diffractometer) and SEM (Scanning Electronic Microscope). By TGA analysis, 88 wt.% mass loss of Mn-PC was found at $419^{\circ}C$. The BET surface area of Mn-PC increased after the pretreatment. The decomposition and combustion of organic components in Mn-PC were observed by EA analysis. We also confirmed that Mn-PC had transformed into a new manganese oxide phase ($Mn_3O_4$) after the pretreatment by XRD analysis. By SEM analysis, many of the micropores generated during the pretreatment were found. The catalytic activity of Mn-PC with the pretreatment for propionaldehyde combustion was higher than that of $Mn_3O_4$ and fresh Mn-PC. It showed the catalytic activity of Mn-PC with the pretreatment for VOCs combustion by the order of toluene < acetadehyde < propionaldehyde.

• 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 the Mineralogical Society of Korea
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• v.26 no.2
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• pp.81-86
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• 2013

A series of birnessite was synthesized at 25, 40, 60, and $80^{\circ}C$, respectively. Intensities of XRD and the ratio of signal to noise of the peaks for samples increases with increasing temperature up to $60^{\circ}C$, whereas the intensity and ratio for a sample synthesized at $80^{\circ}C$ decrease, showing that crystallinity of the birnessite synthesized at $60^{\circ}C$ is better than that of the synthesized at $80^{\circ}C$. However, BET surface areas for these two samples show that the surface area increases 39.4 to 89.7 $m^2/g$ with increasing synthesizing temperature from 60 up to $80^{\circ}C$, indicating that a small surface area is shown in a well-crystallized birnessite rather than that of a poorly crystallized birnessite. SEM images show that morphologies for samples are seriously influenced by temperature. The morphology of the synthesized at 25 shows a round-shape, while a plate-like morphology is shown in the synthesized birnessite at $80^{\circ}C$. In addition, a porous layered structure is also shown in the synthesized birnessite at $80^{\circ}C$. These results suggest that physicochemical properties of the synthesized birnessite are sensitively affected by mechanical changes of parameters such as temperature during the synthesization.

• Journal of the Korean Magnetics Society
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• v.18 no.1
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• pp.24-27
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• 2008

We have prepared $MnFe_2O_4$ nanoparticles with polyol method. The crystallographic and magnetic properties were measured by using X-ray diffraction(XRD), vibrating sample magnetometer(VSM) and $M\"{o}ssbauer$ spectroscopy. The high resolution transmission electron microscope(HRTEM) shows uniform nanoparticle-sizes with $6{\sim}8$ nm. The crystal structure is found to be single-phase cubic spinel with space group of Fd3m. The lattice constant of $MnFe_2O_4$ nanparticles is determined to be $8.418{\pm}0.001{\AA}$. $M\"{o}ssbauer$ spectrum of $MnFe_2O_4$ nanparticles at room temperature(RT) shows a superparamagnetic behavior. In VSM analysis, the diagnosis of the superparamagnetic behavior is also shown in hysteresis loop at RT. $M\"{o}ssbauer$ spectrum at 4.2K shows that the well developed two sextets are with different hyperfine field $H_{hfA}=498$(A-site) and $H_{hfB}=521$(B-site) kOe.

• Journal of the Mineralogical Society of Korea
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• v.32 no.3
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• pp.151-162
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• 2019

Todorokite, a tunnel-structured manganese oxide, can contain cations within the relatively large nanopores created by the $3{\times}3$ Mn octahedra. Because todorokite is poorly crystalline and found as aggregates mixed with other phases of Mn oxides in nature, the coordination structure of cations in the nanopores is challenging to fully characterize in experiment. In the current article, we report the atomistic coordination structures of $Mg^{2+}$ ions in todorokite tunnel nanopores using the classical molecular dynamics (MD) simulations. In experiment, $Mg^{2+}$ is known to occupy the center of the nanopores. In our MD simulations, 60 % of $Mg^{2+}$ ions were located at the center of the nanopores; 40 % of the ions were found at the corners. All $Mg^{2+}$ located at the center formed the six-fold coordination with water molecules, just as the ion in bulk aqueous solution. $Mg^{2+}$ ions at the corners also formed the six-fold coordination with not only water molecules but also Mn octahedral surface oxygens. The mean squared displacements were calculated to examine the dynamic features of $Mg^{2+}$ ions in the one-dimensional (1D) nanopores. Our MD simulations indicate that the dynamic features of water molecules and the cations observed in bulk aqueous solution are lost in the 1D nanopores of todorokite.

• Korean Journal of Soil Science and Fertilizer
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• v.32 no.4
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• pp.327-332
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• 1999

Manganese (Mn) oxides in soils have been a research subject since they react with nutrients and contaminants and Mn itself is an essential element for plant growth. Birnessite was synthesized in the presence of iron (Fe) in the precipitating solution. Influence of Fe, one of common elements in soils, on crytallinity, morphology, and chemical reactivity of birnessite was examined using X-ray diffraction (XRD), electron microscope, canon exchange capacity (CEC), and chromium (Cr) oxidation capacity. With increasing Fe concentration in the precipitating solution, crystallinity and crystal size decreased. Hexagonal plates of the birnessites formed at low Fe concentration were dominant and replaced more and more by aggregate of small particles with increasing the Fe concentration. There is no significant change in CEC with changing the Fe concentration. Chromium oxidation capacity of the birnessite increased with increasing the Fe concentration. Iron in the precipitating solution poisoned crystal growth by adsorption on the surface and increased nucleation. Since Fe is a common constituent under pedogenic environment and Fe and Mn oxides often coexist in Mn oxide nodules, the birnessite with small particle, low crystallinity, and high chemical reactivity is the form which is more likely to be formed in soils. The high CEC ($140cmol_ckg^{-1}$) and oxidation capacity of birnessite indicate that birnessite can be used in environment and agriculture.

• Clean Technology
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• v.29 no.3
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• pp.185-192
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• 2023

This study was conducted to obtain basic process simulation data before conducting pyrolysis experiments for the development of a thermochemical conversion system by recirculation of heat carrier and gases thereby. In this study, polypropylene (PP) was used as a pyrolysis sample material as an alternative to waste plastics, and fluid sand was used as a heat transfer medium in the system. Manganese (Mn) was chosen as the catalyst for the pyrolysis experiment, and the catalyst pyrolysis was performed by impregnating it in the sand. The basic properties of PP were analyzed using a thermogravimetric analyzer (TGA), and liquid oil was generated through catalytic pyrolysis under a nitrogen atmosphere at 600℃. The carbon number distribution of the generated liquid oil was confirmed by GC/MS analysis. In this study, the effects of the presence and the amount of Mn loading on the yield of liquid oil and the distribution of hydrocarbons in the oil were investigated. When Mn/sand was used, the residue decreased and the oil yield increased compared to pyrolysis using sand alone. In addition, as the Mn loading increased, the ratio of C₆~C₉ range gasoline in the liquid oil gradually increased, and the distribution of diesel and heavy oil with more carbon atoms than C₁₀ in the oil decreased. In conclusion, it was found that using Mn as a catalyst and changing the amount of Mn could increase the yield of liquid oil and increase the gasoline ratio in the product.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.1
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• pp.33-40
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• 2023

Todorokite is a manganese oxide mineral containing Mg²⁺ in a tunnel structure in which MnO₆ octahedra share corners. In order to investigate the suitability and efficiency of high temperature-treated todorokite as a material for adsorption and fixation of Cs, Cs was ion exchanged and the amount of leached Cs from todorokite was measured. The todorokite used in this study was synthesized by transforming Na-birnessite to Mg-buserite and used as a precursor. After high temperature treatment, Cs exchanged todorokite changed to birnessite and hausmannite as the temperature increased. The amount of leached Cs was investigated for Cs exchanged todorokite which was reacted with distilled water and 1 M NaCl solution at different reaction times. In general, for the samples reacted with 1 M NaCl solution, the fixation of Cs was quite effective, although the amount of leached Cs was greater due to the ion exchange reaction with Na. As the treatment temperature increased, the amount of leached Cs increased and then decreased again, which was related to the mineral phases formed at each temperature. As birnessite was formed, the amount of leached Cs increased, but as birnessite decreased, that decreased again. As the mineral phase changed to hausemanite, the amount of Cs decreased rapidly. The results of our study show that Cs exchanged todorokite can be used as a material that effectively fixes Cs and prevents its diffusion by high temperature treatment.

• Economic and Environmental Geology
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• v.8 no.3
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• pp.117-124
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• 1975

Wet chemical analysis (for $MnO_2$, MnO, and $H_2O$(+)) and electron microprobe analysis (for $Fe_2O_3$ and PbO) give $MnO_2$ 74.91, MnO 11.33, $Fe_2O_3$ (total Fe) 4.19, PbO 0.03, $H_2O$ (+) 9.46, sum 99.92%. 'Available oxygen determined by oxalate titration method is allotted to $MnO_2$ from total Mn, and the remaining Mn is calculated as MnO. Traces of Ba, Ca, Mg, K, Cu, Zn, and Al were found. Li and Na were not found. The existence of (OH) is verified from the infrared absorption spectra. The analysis corresponds to the formula $Mn^{4+}{_{4.85}}(Mn^{2+}{_{0.90}}Fe^{3+}{_{0.30}})_{1.20}O_{8.09}(OH)_{5.91}$, on the basis of O=14, 'or ideally $Mn^{4+}{_{5-x}}(Mn^{2+},Fe^{3+})_{1+x}O_{8}(OH)_{6}$ ($x{\approx}0.2$). X-ray single crystal study could not be made because of the distortion of single crystals. But the x-ray powder pattern is satisfactorily indexed by an orthorhombic cell with a 9.324, b 14.05, c $7.956{\AA}$., Z=4. The indexed powder diffraction lines are 9.34(s) (100), 7.09(s) (020), 4.62(m) (200, 121), 4.17(m) (130), 3.547(s) (112), 3.212(vw) (041), 3.101(s) (300), 2.597(w) (013), 2.469(m) (331), 2.214(vw)(420), 2.098(vw) (260), 2.014 (vw) (402), 1.863(w) (500), 1.664(w) (314), 1.554(vw) (600), 1.525(m) (601), 1.405(m) (0.10.0). DTA curve shows the endothermic peaks at $250-370^{\circ}C$ and $955^{\circ}C$. The former is due to the dehydration: and oxidation forming$(Mn,\;Fe)_2O_3$(cubic, a $9.417{\AA}$), and the latter is interpreted as the formation of a hausmannite-type oxide (tetragonal, a 5.76, c $9.51{\AA}$) from $(Mn,\;Fe)_2O_3$. Infrared absorption spectral curve shows Mn-O stretching vibrations at $515cm^{-1}$ and $545cm^{-1}$, O-H bending vibration at $1025cm^{-1}$ and O-H stretching vibration at $3225cm^{-1}$. Opaque. Reflectance 13-15%. Bireflectance distinct in air and strong in oil. Reflection pleochroism changes from whitish to light grey. Between crossed nicols, color changes from yellowish brown with bluish tint to grey in air and yellowish brown to grey through bluish brown in oil. No internal reflections. Etching reactions: HCl(conc.) and $H_2SO_4+H_2O_2$-grey tarnish; $SnCl_2$(sat.)-dark color; $HNO_3$(conc.)-grey color; $H_2O_2$-tarnish with effervescence. It is black in color. Luster dull. Cleavage one direction perfect. Streak brownish black to dark brown. H. (Mohs) 2-3, very fragile. Specific gravity 3.59(obs.), 3.57(calc.). It occurs as radiating groups of flakes, flower-like aggregates, colloform bands, dendritic or arborescent masses composed of fine grains in the cementation zone of the supergene manganese oxide deposits of the Janggun mine, Bonghwa-gun, southeastern Korea. Associated minerals are calcite, nsutite, todorokite, and some undetermined manganese dioxide minerals. The name is for the mine, the first locality. The mineral and name were approved before publication by the Commission on New Minerals and Mineral Names, I.M.A.

• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.