• 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.

• Journal of the Korean Magnetic Resonance Society
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• v.14 no.2
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• pp.55-75
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• 2010

An ion-exchanged reaction of $MnCl_2$ with Al-incorporated solid core/mesoporous shell silica (AlSCMS) followed by calcinations generated manganese species, where average oxidation state of manganese ion is 3+, in the mesoporous materials. Dehydration results in the formation of $Mn^{2+}$ ion species, which can be characterized by electron spin resonance (ESR). The chemical environments of the manganese centers in Mn-AlSCMS were investigated by diffuse reflectance, UV-VIS and ESR spectroscopic methods. Upon drying at 323 K, part of manganese is oxidized to higher oxidation state ($Mn^{3+}$ and $Mn^{4+}$) and further increase in (average) oxidation state takes place upon calcinations at 823 K. It was found that the manganese species on the wall of the Mn-AlSCMS were transformed to tetrahedral $Mn^{3+}$ or $Mn^{4+}$ and further changed to square pyramid by additional coordination to water molecules upon hydration. The oxidized $Mn^{3+}$ or $Mn^{4+}$ species on the surfaces were reversibly reduced to $Mn^{2+}$ or $Mn^{3+}$ species or lower valances by thermal process. Mn(II) species I with a well resolved sextet was observed in calcined, hydrated Mn-AlSCMS, while Mn (II) species II with g = 5.1 and 3.2 observed in dehydrated Mn-AlSCMS. Both species I and II are considered to be non-framework Mn(II).

• Korean Journal of Materials Research
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• v.33 no.7
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• pp.315-322
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• 2023

In the present work, we address the new route for the green synthesis of manganese dioxide (MnO₂) by an innovative method named the solution plasma process (SPP). The reaction mechanism of both colloidal and nanostructured MnO₂ was investigated. Firstly, colloidal MnO₂ was synthesized by plasma discharging in KMnO₄ aqueous solution without any additives such as reducing agents, acids, or base chemicals. As a function of the discharge time, the purple color solution of MnO₄^- (oxidation state +7) was changed to the brown color of MnO₂ (oxidation state +4) and then light yellow of Mn²⁺ (oxidation state +2). Based on the UV-vis analysis we found the optimal discharging time for the synthesis of stable colloidal MnO₂ and also reaction mechanism was verified by optical emission spectroscopy (OES) analysis. Secondly, MnO₂ nanoparticles were synthesized by SPP with a small amount of reducing sugar. The precipitation of brown color was observed after 8 min of plasma discharge and then completely separated into colorless solution and precipitation. It was confirmed layered type of nanoporous birnessite-MnO₂ by X-ray powder diffraction (XRD), fourier-transform infrared spectroscopy (FT-IR), and electron microscopes. The most important merits of this approach are environmentally friendly process within a short time compared to the conventional method. Moreover, the morphology and the microstructure could be controllable by discharge conditions for the appropriate potential applications, such as secondary batteries, supercapacitors, adsorbents, and catalysts.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2006.09b
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• pp.1220-1221
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• 2006

[ $LiMn_2O_4$ ] powders for lithium ion batteries were synthesized from two separate raw material pairs of LiOH/MnO and $LiOH/MnO_2$. The powders prepared at 780 and $850^{\circ}C$ and their difference of electrochemical properties were investigated. Both powders calcined at 780 and $850^{\circ}C$ were composed of a single-phase spinel structure but those treated at $850^{\circ}C$ showed a lower intensity ratio of $I_{311}$ to $I_{400}$, a slightly larger lattice parameter, and an increased discharge capacity by 10% under $3.0{\sim}4.3V$ voltage range. The XPS study on the oxidation states of manganese repealed that powders made from LiOH/MnO had less $Mn^{3+}$ ion and gave better battery performances than those from $LiOH/MnO_2$.

• Journal of Korean Society on Water Environment
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• v.35 no.3
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• pp.271-277
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• 2019

Korean Trophic State Index ($TSI_{KO}$) was developed in 2006, and was composed of COD ($COD_{Mn}$ based on permanganate method), Chlorophyll a (Chl.a) and total phosphorus (TP). However, $COD_{Mn}$ usually represents only 50-60% of total organic matter in stream or lake water due to low oxidizing power of permanganate. This study investigated the relationship between TOC and $COD_{Mn}$ based on the average data for the whole layer in 81 lakes in Korea, during the period 2013-2017. As a result, $COD_{Mn}$ was found to be 1.54 times more than TOC in 66 of the freshwater lakes and 3 brackish lakes (TOC measured using thermo-oxidation method). TOC was about a quarter of $COD_{Mn}$ in 8 coastal lakes (TOC measured using UV-persulfate oxidation method), and it appeared to be underestimated due to chloride interference. Using the data of 69 lakes with exception of 12 brackish lakes, $TSI_{KO}$(TOC) was developed based on the correlation between TOC and $COD_{Mn}$, while $TSI_{KO}$(COD) was replaced with $TSI_{KO}$(TOC). However, for trophic state assessment of brackish lakes, the $TSI_{KO}$(TOC) can only be utilized in case that TOC is measured through thermo-oxidation method. The determination coefficient of $TSI_{KO}$(Chl) to $TSI_{KO}$(COD) in 66 freshwater lakes and 3 brackish lakes was 0.83, while that to $TSI_{KO}$(TOC) was 0.68. This difference could be attributed to the recalcitrant organic part of TOC.

• Journal of the Korean Ceramic Society
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• v.37 no.4
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• pp.338-344
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• 2000

Grain boundary chemistry and electrical characteristics of polycrystalline BaTiO3 ceramics, which were prepared with sol-gel surface-coated semiconducting powders, were investigated. Mn ions were coated on the powder surface by sol-gel coating-techniques. The additives coated on the surface of the powders were observed to be present near the grain boundaries of the ceramics. The ceramics exhibit the PTCR characteristics with a resistivity jump ratio(Pmax/Pmin) of about 2$\times$103. With raising the temperature from room temprature to 20$0^{\circ}C$, the oxidation state of the Mn ions varied from Mn3+ to Mn2+ in the coating layers. Near the grain boundaries an excessive negative charge layer of about 20nm was formed.

• Korean Chemical Engineering Research
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• v.44 no.2
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• pp.193-199
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• 2006

The catalytic oxidation of toluene over $-Al_2O_3$ supported copper-manganese oxide catalysts in the temperature range of $160-280^{\circ}C$ was investigated by employing a fixed bed flow reactor. The catalysts were characterized by BET, scanning electron microscopy (SEM), temperature-programmed reduction(TPR), temperature-programmed oxidation(TPO), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction(XRD) techniques. Catalytic oxidation of toluene was achieved at the below $280^{\circ}C$, and the optimal content of copper and manganese in the catalyst was found to be 15.0 wt％Cu-10.0 wt％Mn. From the TPR/TPO and XPS results, the redox peak of 15 Cu-10 Mn catalyst shifted to the lower temperature, and the binding energy was shifted to the higher binding energy. Furthermore, It is considered that $Cu_{1.5}Mn_{1.5}O_4$ is superior to Mn oxides and CuO in the role as active factor of catalysts from the XRD results and also catalytic activities are dependent on the redox ability and high oxidation state of catalysts.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.303-312
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• 2023

The determination of the oxidation states of metal elements in manganese nodules sheds light on the understanding of the formation mechanism of nodules, providing insights into the paleo-environmental conditions such as the redox potential of the aqueous system. This study aims to reveal the oxidation states and chemical bonding of manganese in the natural polymetallic nodules, utilizing conventional X-ray photoelectron spectroscopy (XPS). Specifically, shallow manganese nodules from the Siberian Arctic Sea, effectively recording mineralogical variations, were used in this study. Detailed analysis of XPS Mn 2p spectra showed changes in the manganese oxidation state from the center to the outer parts of the nodules. The central part of the nodules showed a higher Mn⁴⁺ content, approximately 67.9%, while the outermost part showed about 63% of Mn⁴⁺ due to an increase in the Mn³⁺+Mn²⁺. The decrease in the Mn oxidation state with the growth is consistent with the previously reported mineralogical variations from todorokite to birnessite with growth. Additionally, the O 1s spectra presented a predominance of Mn-O-H bonds in the outer layers compared to the center, suggesting hydration by water in the layered manganates of outer layers. The results of this study demonstrate that XPS can be directly applied to understand changes in paleo-environmental conditions such as the redox states during the growth of manganese nodules. Finally, future studies using high-resolution synchrotron-based XPS experiments could achieve details in oxidation states of manganese and trace metal elements.

• Clean Technology
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• v.16 no.2
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• pp.132-139
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• 2010

The Cu-Mn mixed oxide catalysts with different molar ratios of Cu/(Cu+Mn) prepared by co-precipitation method have been investigated in CO oxidation at $30^{\circ}C$. The catalysts used in this study were characterized by X-ray Diffraction (XRD), $N_2$ sorption, X-ray photoelectron spectroscopy (XPS), and $H_2$-temperature programmed reduction $(H_2-TPR)$ to correlate with catalytic activities in CO oxidation. The $N_2$ adsorption-desorption isotherms of Cu-Mn mixed oxide catalysts showed a type 4 having pore range of 7-20 nm and BET surface area was increased from 17 to $205\;m^2{\cdot}g^{-1}$ with increasing of Mn content. The XPS analysis showed the surface oxidation state of Cu and Mn represented $Cu^{2+}$and the mixture of $Mn^{3+}$ and $Mn^{4+}$, respectively. Among the catalysts studied here, Cu/(Cu+Mn) = 0.5 catalyst showed the highest activity at $30^{\circ}C$ in CO oxidation and the catalytic activity showed a typical volcano-shape curve with respect to Cu/(Cu+Mn) molar ratios. The water vapor showed a prohibiting effect on the efficiency of the catalyst which is due to the competitive adsorption of carbon monoxide on the active sites of catalyst surface and finally the formation of hydroxyl group with active metals.

• 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.