• Korean Journal of Materials Research
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• v.32 no.8
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• pp.339-344
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• 2022

The lattice oxygen mechanism (LOM) is considered one of the promising approaches to overcome the sluggish oxygen evolution reaction (OER), bypassing -OOH^* coordination with a high energetic barrier. Activated lattice oxygen can participate in the OER as a reactant and enables O^*-O^* coupling for direct O₂ formation. However, such reaction kinetics inevitably include the generation of oxygen vacancies, which leads to structural degradation, and eventually shortens the lifetime of catalysts. Here, we demonstrate that Se incorporation significantly enhances OER performance and the stability of NiFe (oxy)hydroxide (NiFe) which follows the LOM pathway. In Se introduced NiFe (NiFeSe), Se forms not only metal-Se bonding but also Se-oxygen bonding by replacing oxygen sites and metal sites, respectively. As a result, transition metals show reduced valence states while oxygen shows less reduced valence states (O^-/O₂^2-) which is a clear evidence of lattice oxygen activation. By virtue of its electronic structure modulation, NiFeSe shows enhanced OER activity and long-term stability with robust active lattice oxygen compared to NiFe.

• Korean Journal of Materials Research
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• v.16 no.5
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• pp.323-328
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• 2006

In situ electrical conductivity measurements on $V_2O_5WO_3/TiO_2$ catalysts were carried out at between 100 and $300^{\circ}C$ under pure oxygen, NO and $NH_3$ to investigate the reaction mechanism for ammonia SCR (selective catalytic reduction) de NOX. The electrical conductivity of catalysts changed irregularly with supply of NO. It was, however, found that the electrical conductivity change with ammonia supply was regular and the increase of electrical conductivity was mainly caused by reduction of the labile surface oxygen. The electrical conductivity change of catalysts showed close relationship with the conversion rate of NOx. Variation of conversion rate in atmosphere without gaseous oxygen also showed that labile lattice oxygen is indispensable in the initial stage of the de NOx reaction. These results suggest that liable lattice oxygen acts decisive role in the de NOx mechanism. They also support that de NOx reaction occurs through the Eley?Rideal type mechanism. The amount of labile oxygen can be estimated from the measurement of electrical conductivity change for catalysts with ammonia supply. This suggests that measurement of the change can be used as a measure of the de NOx performance.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.37 no.4
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• pp.358-373
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• 2024

Oxygen evolution reaction is a critical bottleneck for the development of efficient electrochemical hydrogen production because of its sluggish reaction. Among various catalysts, transition metal-based layered double hydroxide has drawn significant attention due to their excellent catalytic properties and cost-effectiveness. This paper begins with basic crystal structures, and then conventional adsorbate evolution mechanism of layered double hydroxide. Strategies for enhancing catalytic properties based on adsorbate evolution mechanism and lattice oxygen mechanism that could surpass theoretical limit of adsorbate evolution mechanism are discussed. This paper ends with a brief discussion on the challenges and future directions of layered double hydroxide-based oxygen evolution reaction catalysts.

• Applied Chemistry for Engineering
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• v.31 no.4
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• pp.368-376
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• 2020

In this study, an analysis on the reaction characteristics of a catalyst using platinum (Pt) as an active oxidation metal catalyst for controlling SO₂ was performed. Pt/TiO₂ catalyst was prepared by using Pt as various precursor forms on a titania (TiO₂) support, and used for the experiment. There was no difference in performance of SO₂ oxidation according to Pt valence states such as Pt²⁺ or Pt⁴⁺ on Pt/TiO₂, and Pt chloride species such as PtCl_x reduces SO₂ oxidation performance. In addition, as a result of analyzing the valence state of the catalyst before and after the SO₂ oxidation reaction by XPS analysis, a decrease in lattice oxygen and an increase in surface chemisorbed oxygen after the SO₂ oxidation reaction were confirmed. Therefore it can be suggested that the oxidation reaction of SO₂ when using the Pt/TiO₂ catalyst is the major one following the Mar-Van Krevelen mechanism where the reaction of lattice oxygen corresponding to PtOx and the oxidation-reduction reaction by oxygen vacancy occur. Overall, it can be confirmed that the oxygen species of PtOx (Pt²⁺ or Pt⁴⁺) present on the catalyst acts as a major active site.

• Bulletin of the Korean Chemical Society
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• v.15 no.8
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• pp.616-622
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• 1994

The oxidation of carbon monoxide by gaseous oxygen in the presence of a powdered $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution as a catalyst has been investigated in the temperature range from 150$^{\circ}$C to 300$^{\circ}$C under various CO and $O_2$ partial pressures. The site of Sr substitution, nonstoichiometry, structure, and microstructure were studied by means of powder X-ray diffraction and infrared spectroscopy. The electrical conductivity of the solid solution has been measured at 300$^{\circ}$C under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-and 1.2-order kinetics with and without a $CO_2$ trap, respectively; first-and 0.7 order with respect to CO and 0.5-order to $O_2$. For the above reaction temperature range, the activation energy is in the range from 0.25 to 0.35 eV/mol. From the infrared spectroscopic, conductivity and kinetic data, CO appears essentially to be adsorbed on the lattice oxygens of the catalyst, while $O_2$ adsorbs as ions on the oxygen vacancies formed by Sr substitution. The oxygen vacancy mechanism of the CO oxidation and the main defect of $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution are supported and suggested from the agreement between IR data, conductivities, and kinetic data.

• Bulletin of the Korean Chemical Society
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• v.8 no.5
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• pp.389-393
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• 1987

The oxidation of carbon monoxide by gaseous oxygen on 0.53, 1.02, and 1.51 mol $\%$CoO-doped $-Fe_2O_3$ catalysts has been investigated in the temperature range from 340 to 480$^{\circ}C$ under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-order kinetics; the 0.5-order with respect to $O_2$ and the first-order with respect to CO. In the above temperature range, the activation energy is 0.34 $\pm$ 0.01 eV${\cdot}$$mol^{-1}$. The electrical conductivity of 0.53, 1.02, and 1.51 mol %CoO-doped $\alpha$-$Fe_2O_3$ has been measured at 350$^{\circ}C$ under various $P_{CO}and $P_{O_2}$. From the conductivity data it was found that $O_2$ was adsorbed on Vo formed by doping with CoO, while CO appeared essentially to be chemisorbed on the lattice oxygen of the catalyst surface. The proposed oxidation mechanism and the dominant defect were supported by the agreement between the kinetic data and conductivities.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.8 no.3
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• pp.401-406
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• 1998

For the applications in optical waveguides and devices, LiNbO_3$ single crystals need to overcome the weakness of optical damage due to the inhomogeneities of laser-induced refractive index. This problem can be solved by doping of Mg in LiNbO_3$ and proton exchange of LiNbO_3$. In this study, to understand the mechanism of optical damage resistance in LiNbO_3$, the changes of lattice defects in LiNbO_3$ caused by MgO doping and acid treatment were observed indirectly by $OH^-$ absorption bands using a FT-IR spectrophotometer. The effect of lattice defects on temperature, heat-treatment and polishing were also investigated. It is shown that MgO doping increases optical damage resistance by generating the defects of $Mg_{Nb}^{2+}$ in the lattice of LiNbO_3$, and that proton exchange by implantation of $H^+$ ion in the hexagonally closest packed oxygen layers on the surface of LiNbO_3$, makes lattice defects, which diffuse into the crystal after heat-treatment above $400^{\circ}C$.

• Journal of Electrochemical Science and Technology
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• v.9 no.3
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• pp.212-219
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• 2018

Perovskite type ceramic membranes which exhibit dual ion conduction (proton and oxygen ion conduction) can permeate water and can aid solving operational problems such as temperature gradient and carbon deposition associated with a working solid oxide fuel cell. From this point of view, it is crucial to reveal water transport mechanism and especially the nature of the surface sites that is necessary for water incorporation and evolution. $BaCe_{0.8}Y_{0.2}O_{3-{\alpha}}$ (BCY20) was used as a model proton and oxygen ion conducting membrane in this work. Four different catalytically modified membrane configurations were used for the investigations and water flux was measured as a function of temperature. In addition, CO was introduced to the permeate side in order to test the stability of membrane against water and $CO/CO_2$ and post operation analysis of used membranes were carried out. The results revealed that water incorporation occurs on any exposed electrolyte surface. However, the magnitude of water permeation changes depending on which membrane surface is catalytically modified. The platinum increases the water flux on the feed side whilst it decreases the flux on the permeate side. Water flux measurements suggest that platinum can block water permeation on the permeate side by reducing the access to the lattice oxygen in the surface layer.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.07a
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• pp.13-17
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• 2002

Ga$_2$O$_3$ nanomaterials were synthesized from mechanically ground GaN powders with thermal annealing Ga$_2$O$_3$ nanobelts were farmed in a nitrogen atmosphere, while Ga$_2$O$_3$ nanoparticles were formed inan oxygen atmosphere. The structural properties of the Ga$_2$O$_3$ nanomaterials were investigated by X-ray diffractometer (XRD) and high-resolution transmission eleotron microscope (HRTEM). The study of field emission scanning electron microscopy (FESEM) on the microstructures of nanomaterials revealed that the nanobelts are with the range of about 10∼200nm width and 10∼50nm thickness, and that nanoparticles are with the range of about 20∼50nm radius. On the basis of XRD and HRTEM data, we determined that the nanobelts grow toward a direction perpendicular to the (010) lattice plane and that they are enclosed by facets of the (10T) and (101) lattice planes. The formation of the nanobelts may be described by the vapor-solid(VS) mechanism, and the supersaturation device of gaseous phase may play an important role in the formation of Ga$_2$O$_3$ nanomaterials.

• Journal of Powder Materials
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• v.13 no.2 s.55
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• pp.112-118
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• 2006

[ $R_{1/3}Sr_{2/3}FeO_{3}$ ](R=Pr, Nd, and Sm) was synthesized and their magnetic properties and charge ordering(CO) transition related with lattice dynamics and oxygen vacancy were systematically investigated. The charge disproportion ation(CD) in $R_{1/3}Sr_{2/3}FeO_{3}$(R=Pr,Nd) was in which two kins of iron with valence state $Fe^{3+}$ and $Fe^{5+}$ were found with ratio of 2:1. In this charge ordering state a sequence of $Fe^{3+}Fe^{3+}Fe^{5+}Fe^{3+}Fe^{3+}Fe^{5+}$ exists aligned along the [111] direction of the pseudocubic perovskite structure. The charge ordering exist in distorted structure involving $t_{pd}$ hybridization. The disordering phases coexist in distorted structure as temprature in creases that is controlled amount of oxygen vacancy. The magnetic hyperfine fields indicate charge tranfering temperature as it dissapeared drastically.