• Title/Summary/Keyword: $Mn^{3+}$

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Study on the reducibility of substituted $LaMnO_3$ (치환된 $LaMnO_3$의 환원반응성에 대한 연구)

  • Lee, Sang-Beom;Jeon, Hyun-Pyo
    • The Journal of Natural Sciences
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    • v.14 no.2
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    • pp.41-54
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    • 2004
  • $LaMnO_3$ and A site substituted $La_{0.9}Sr_{0.1}MnO_3$(a=$5.33\AA$, c=$13.27\AA$), B site substituted $LaMn_{0.9}Cu_{0.1}O_3$(a=$5.52\AA$, c=$13.31\AA$) mixed oxides were prepared by Citrate sol-gel method. The powder X-ray diffraction patterns of these oxides were indexed with single phase hexagonal perovskite structures. According to the TRR result, oxygen stoichiometry of these oxides were oxidative nonstoichiometry as like $LaMnO_{3.16}$, $La_{0.9}Sr_{0.1}MnO_{3.10}$ and $LaMn_{0.9}Cu_{0.1}O_{3.14}$ Reduction reactions of un-substituted $LaMnO_3$ was two steps, but specific site(A site of B site) partially substituted $LaMnO_3$ oxides were procees to three reactions.

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XMCD and PES study of a compensated-ferrimagnetic half-metal Mn3Ga

  • Seong, Seungho;Lee, Eunsook;Kim, Hee Yeon;Kim, Younghak;Baik, Jaeyoon;Kang, J.S.
    • Current Applied Physics
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    • v.18 no.11
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    • pp.1190-1195
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    • 2018
  • By employing soft X-ray magnetic circular dichroism (XMCD), soft X-ray absorption spectroscopy (XAS), and photoemission spectroscopy (PES), we have investigated the electronic structure of the candidate zero-moment half-metallic $Mn_3Ga$. We have studied the ball-milled and annealed $Mn_3Ga$ powder samples that exhibit nearly zero magnetization. Mn 2p XAS revealed that Mn ions in $Mn_3Ga$ are nearly divalent for both of the Mn ions having the locally octahedral symmetry and those having the locally tetrahedral symmetry. The measured Mn 2p XMCD spectrum of $Mn_3Ga$ is very similar to that of ferrimagnetic $MnFe_2O_4$ having divalent Mn ions. The sum-rule analysis of the Mn 2p XMCD spectrum shows that both the spin and orbital magnetic moments of Mn ions in $Mn_3Ga$ are negligibly small, in agreement with the nearly compensated-ferrimagnetic ground state of $Mn_3Ga$. The valence-band PES spectrum of $Mn_3Ga$ agrees well with the calculated density of states, supporting the half-metallic electronic structure of $Mn_3Ga$.

Effects of $Mn_2O_3, Y_2O_3$ Additives and Valence State of Mn ion in $Sr(Zr, Ti)O_3$ Microwave Dielectrics ($Sr(Zr, Ti)O_3$ 마이크로파 유전체에 첨가된 $Mn_2O_3, Y_2O_3$ 의 영향과 Mn의 산화상태)

  • 정하균;박도순;박윤창
    • Journal of the Korean Ceramic Society
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    • v.34 no.6
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    • pp.583-590
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    • 1997
  • The effects of Mn2O3 and Y2O3 additives on the microstructure and dielectric properties of Sr(Zr, Ti)O3 have been investigated. Powders with Sr(Zr1-xTix)O3(0$\leq$x$\leq$0.1) composition were prepared by the conventional solid state processing from commercial TiO2 and precipitation-processed ZrO2. The powders containing sintering additives of Mn2O3 and Y2O3 were compacted and then sintered at 1,55$0^{\circ}C$ for 4 h to get>97% relative density. Mn2O3 suppressed the grain growth and Y2O3 enhanced the density of sintered body. The oxidation state of Mn ions were determined by a chemical wet method and EPR spectroscopy. Mn ions were present as Mn2+ and Mn4+ in SrZrO3, while as Mn3+ and Mn4+ in Ti-substituted Sr(Zr, Ti)O3. With the substitution of Ti, the lattice parameters of SrZrO3 decreased and its dielectric constant increased with remarkable decrease in Q value. The dielectric constant of Sr(Zr, Ti)O3 was in the range of 30 to 40, Q values 1,200~5,400 at 6 GHz and temperature coefficient of resonant frequency -67~100 ppm/K.

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Determination of Mn Oxidation State in Mn-(hydr)oxides using X-ray Photoelectron Spectroscopy(XPS) (X-선 광전자 분광법을 이용한 망간산화물의 망간 산화상태 해석)

  • Song, Kyung-Sun;Bae, Jong-Seong;Lee, Gie-Hyeon
    • Economic and Environmental Geology
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    • v.42 no.5
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    • pp.479-486
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    • 2009
  • In natural environments, manganese (Mn) exists in the valence of +2, +3, and +4 and plays a pivotal role as a strong oxidant or reductant in the geochemical cycles of elements. Especially, Mn forms varying (oxyhydr)oxides. The oxidation state of structural Mn is characteristic to each oxide and is one of the most important factors controlling its geochemical behaviors such as solubility, sorption capacity, and redox potential. Therefore, it is important to elucidate processes governing Mn oxidation state in predicting the fate and transport of many redox sensitive elements in the environment. X-ray photoelectron spectroscopy (XPS) is a very useful method to determine the oxidation state of various elements in solid phases. In this study, the oxidation states of structural Mn in MnO, $Mn_2O_3$, $MnO_2$ were assessed based on the binding energy spectra of $Mn2p_{3/2}$ and Mn3s using XPS and were compared with those reported elsewhere. $Mn2p_{3/2}$ binding energies were determined as 640.9, 641.5, 641.8 eV for MnO, $Mn_2O_3$, $MnO_2$, respectively, which indicates that the binding energy increased with increasing Mn oxidation state. It was also noted that Ar etching may cause changes in electronic structure configuration on surface of the original sample.

X-ray Photoemission Spectroscopy Study of Cation-Deficient La$_{0.970}$Mn$_{0.970}$O$_3$ System (양이온 결손 La$_{0.970}$Mn$_{0.970}$O$_3$의 X-ray Photoemission Spectroscopy 관측)

  • 정우환
    • Journal of the Korean Ceramic Society
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    • v.36 no.1
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    • pp.50-54
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    • 1999
  • We have measured the x-ray photoemission spectroscopy of cation deficient La0.970Mn0.970O3 as a function of temperature. Detailed results on the chemical shifts and changes in Mn 2p and Lp 3d core levels due to variation of temperature have been obtained. The Mn 2p 3/2 and 1/2 main peaks and La 3d core spectrum shift to lower binding energy levels with increasing temperature. This XPS behavior is correlated with the strength of localization of Mn3+. The Jahn-Teller effect due to Mn3+ besides the conventional random potential effects is likely to localize charge carriers in La-.970Mn0.970O3.

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Comparison of Removal Efficiency of Mn-loaded Natural Zeolites and Red Mud for the Catalytic Ozonation of 2-Butanone

  • Park, Youna;Lee, Jung Eun;Park, Young-Kwon
    • Applied Chemistry for Engineering
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    • v.33 no.3
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    • pp.328-334
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    • 2022
  • For the study of environmental application of natural zeolites (NZ) and red mud (RM), which are discharged from various industrial fields, the catalytic ozonation of 2-butaone (methyl ethyl ketone, MEK) was performed using the Mn-loaded NZ prepared according to the Mn content of 1, 3, 5, 7, and 10 wt%. By the addition of Mn to NZ, the BET (Brunaure-Emmett-Teller) specific surface area of Mn/NZ catalysts decreased while the ratio of Mn3+/[Mn3++Mn4+] intensively increased. Besides, the addition of Mn component to NZ increased the ratio of adsorbed oxygen (Oadsorbed) toward lattice oxygen (Olattice), Oadsorbed/Olattice from 0.076 of NZ to 0.465 of 10 wt% Mn/NZ according to the amount of Mn. It is known that the proportion of two species, Mn3+ and Oadsorbed, would greatly affect the catalytic activity. However, the balancing between the paired species, Mn3+ vs. Mn4+ and Oadsorbed vs. Olattice might be more essential for the catalytic ozonation of MEK at room temperature. Among the Mn-loaded NZ catalysts, the 3 wt% Mn/NZ showed the best activity for the removal of MEK and ozone. The 5, 7, and 10 wt% Mn/NZ catalysts are slightly inferior to the 3 wt% Mn/NZ. Compared to the pristine NZ, the Mn/NZ catalysts showed better activity for the catalytic ozonation of MEK. In addition, the 3 wt% Mn/NZ was confirmed to have the most available acid sites among them by the analysis of NH3-TPD (temperature programmed desorption). This might be the major reason for the best catalytic activity of 3 wt% Mn/NZ together with the adjusted distribution ratios of Mn3+/Mn4+ and Oadsorbed/Olattice. Considering the result of 3 wt% Mn/NZ, the 3 wt% Mn/RM was prepared to perform the catalytic activity for the removal of MEK and ozone, but the efficiency of 3 wt% Mn/RM was significantly lower than that of the 3 wt% Mn/NZ.

Synthesis of Cobalt Oxide Free Black Color Spinel Pigment (CoO가 첨가되지 않은 스피넬계 흑색안료의 합성)

  • Kim, Jun-Ho;Lee, Seong-Ho;Suh, Man-Chul;Lee, Byung-Ha
    • Journal of the Korean Ceramic Society
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    • v.44 no.11
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    • pp.639-644
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    • 2007
  • Spinel pigments, developing black color in high temperature glazes at oxidation or reduction atmosphere, without CoO because of its high price were synthesized by solid solution method. Ten mixed compositions consisted of NiO, MnO, $Fe_2O_3 and $Mn_2O_3$ were fired at $1250^{\circ}C$ for 1h. The resulting pigments were characterized by using XRD, FT-IR, SEM and UV-vis spectrometer. Structure of the pigments are spinel and particles' shape are spherical or cubic. Glazed tiles containing 5 wt% pigments were fired at $1260^{\circ}C$ and $1240^{\circ}C$ in reduction atmosphere. Color in glazes were analyzed by UV-vis spectrometer. Colors of NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0125 mole% and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole% in lime glaze showed black in oxidation, in reduction NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0125 mole% and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.55{\cdot}Mn_2O_3$ 0.0125 mole% showed black. In case of lime-barium glaze, NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole%, NiO 0.975 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% and NiO 0.925 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% showed black color in oxidation and NiO 0.875 MnO $0.125{\cdot}Fe_2O_3$ $0.3875{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.1125 mole%, NiO 0.925 MnO $0.075{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% and NiO 0.725 MnO $0.275{\cdot}Fe_2O_3$ $0.4375{\cdot}Cr_2O_3$ $0.50{\cdot}Mn_2O_3$ 0.0625 mole% showed black one in reduction.

Removal of As(III) and Phenol by Multi-functional Property of Activated Carbon Impregnated With Manganese (망간첨착 활성탄의 다기능성을 이용한 3가 비소 및 페놀 제거)

  • Yu, Mok-Ryun;Hong, Soon-Chul;Yang, Jae-Kyu;Chang, Yoon-Young
    • Journal of Soil and Groundwater Environment
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    • v.13 no.3
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    • pp.52-58
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    • 2008
  • Mn-impregnated activated carbon (Mn-AC) prepared at different conditions was applied in the treatment of synthetic wastewater containing both organic and inorganic contaminants. Phenol and As(III) was used as the representative organic and inorganic contaminants, respectively. After evaluation of the physicochemical characteristic and stability of Mn-AC, oxidation of As(III) as well as adsorption of phenol by activated carbon(AC) and Mn-AC were investigated in a batch reactor. To investigate the stability of Mn-AC, dissolution of Mn from each Mn-AC was measured pH ranging from 2 to 4. Although Mn-AC was unstable at a strong acidic condition, the dissoluted Mn was below 3 ppm at pH 4. XRD analysis of Mn-AC indicated that the mineral type of the impregnated manganese was $Mn_2O_3$. From the simultaneous treatment of As(III) and phenol by AC and Mn-AC, As(III) oxidation by Mn-AC was greater than that by AC at lower pH, while the reverse order was observed at higher pH. After impregnation of Mn onto AC, 13% decrease of the surface area was observed, causing 8% reduction of phenol removal. Considering removal properties of As(III) and phenol, Mn-AC could be applied in the simultaneous treatment of wastewater contaminated with multi-contaminants.

XPS Study of Mn 2pp and 3s Satellite Structures of Heusler Alloys: NiMnSb, ppdMnSb, pptMnSb

  • Yang, See-Hun;Oh, Se-Jung;ppark, Je-Geun
    • Proceedings of the Korean Vacuum Society Conference
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    • 1994.02a
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    • pp.50-50
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    • 1994
  • Half-metallic Heusler alloys (NiMnSb, ppdMnSb, pptMnSb) have attracted much attention due to their unique electronic and magnetic structures. Sppin-ppolarized band structure calculation ppredicts metallic behavior for the majority sppin states and semiconductor behavior for the minority sppin states. We have studied the electronic structures of these half-metallic Heusler alloys by core-level pphotoemission sppectroscoppy of Mn 2pp and 3s XppS sppectra. We found large intensities of Mn 2pp satellites and 3s exchange spplitting comppared with other metal Mn-alloys. These satellite structure can be understood by applying Anderson imppurity model. This fact supports the calculated sppin pprojected ppartial density of states which suggests that the valence electrons be highly sppin ppolarized near Fermi level and that the electrons involved with charge-transfer be mainly minority sppin ones which have semiconducting band structure. The trend of charge transfer energies Δ from ligands (Sb 5pp) to Mn 3d, obtained from our model fitting, is consistent with that calculated from sppin pprojected ppartial density of state. Also the trend of d-d electron correlation energies U calculated from Mn Auger line L3 VV by Mg $K\alpha$ source is comppatible with that resulted from our model fitting. We fitted the Mn 3s curve in the same way as for insulating Mn comppounds by using the same pparameters calculated from Mn 2pp curve fitting exceppt for the Coulomb interaction energy Q between core hole and d-electrons. The 3s sppectra were analyzed by combing the charge transfer model and a simpple model taking into account the configuration mixing effect due to the intra-shell correlation. We found that the exchange interaction between 3s hole and 3d electrons is mainly respponsible for the satellite of Mn 3s sppectra. This is consistent with the neutron scattering data, which suggests local 3d magnetic moment. We find that the XppS analysis results of Mn 2pp and 3s satellite structures of half-metallic Heusler alloys are very similar to those of insulating transition metal comppounds.

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First-principles Study on the Magnetism and Electronic Structure of (CrAs)3(MnAs)3(110) Superlattice ((CrAs)3(MnAs)3(110) 초격자의 전자구조와 자성에 대한 제일원리 연구)

  • Lee, J.I.;Hong, S.C.
    • Journal of the Korean Magnetics Society
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    • v.16 no.2
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    • pp.111-114
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    • 2006
  • We investigated the magnetism and electronic structures for the layered structures consisting of (110) layers of zinc-blende CrAs and MnAs. We calculated the electronic structures for $(CrAs)_3(MnAs)_3(110)$ superlattice consisted of alternating three layers of CrAs(110) and MnAs(110) by the full-potential linearized augmented plane wave (FLAPW) method. The calculated magnetic moment of Cr in interface layer ($3.07\;\mu_B$) was slightly larger than that of Cr atom in center layer ($3.06\;\mu_B$), while that of interface Mn atom ($3.74\;\mu_B$) was slightly smaller than the value of Mn atom in center layer ($3.76\;\mu_B$). The electronic structure and half-metallicity in this superlattice were discussed using the calculated density of states.