• 한국재료학회지
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• 제32권8호
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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.

• 한국재료학회지
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• 제16권5호
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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.

• 한국전기전자재료학회논문지
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• 제37권4호
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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.

• 공업화학
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• 제31권4호
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• pp.368-376
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• 2020

본 연구에서는 SO₂를 제어하기 위한 산화 촉매에서 platinum (Pt)을 활성금속으로 하는 촉매의 반응특성에 관한 분석을 수행하였다. Titania (TiO₂) 지지체에 다양한 precursor 형태의 Pt를 사용하여 Pt/TiO₂ 촉매를 제조하여 실험에 사용하였다. Pt/TiO₂ 상의 Pt²⁺ 또는 Pt⁴⁺와 같은 Pt valence state에 따른 SO₂ 산화의 성능 차이는 나타나지 않으며, PtCl_x과 같은 Pt chloride species는 전체적으로 SO₂ 산화 성능을 감소시킨다. 또한, XPS 분석을 수행하여 SO₂ 산화 반응 전/후의 촉매상의 valence state를 분석한 결과 SO₂ 산화반응 이후 lattice oxygen의 감소 및 surface chemisorbed oxygen의 증가를 확인할 수 있다. 따라서 Pt/TiO₂ 촉매의 SO₂의 산화 반응은 PtOx에 해당하는 lattice oxygen의 반응과 oxygen vacancy에 의한 산화-환원 반응이 진행되는 Mar-Van Krevelen 메커니즘이 주요한 SO₂ 산화 반응임을 판단할 수 있으며, 이러한 결과를 통하여 촉매 상에 존재하는 PtOx (Pt²⁺ 또는 Pt⁴⁺)의 oxygen species가 주요한 활성 site로 작용함을 확인할 수 있다.

• Bulletin of the Korean Chemical Society
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• 제15권8호
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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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• 제8권5호
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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.

• 한국결정성장학회지
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• 제8권3호
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• pp.401-406
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• 1998

LiNbO_3$ 단결정의 광학소자 광도파관 등의 응용을 위하여는 빛의 조사에 따라 굴절률이 변하는 광손상을 극복하여야 한다. 이러한 광손상 극복은 LiNbO_3$ 에 MgO를 첨가한 단결정의 성장과 산처리를 통하여 가능하다. 본 연구에서는 LiNbO_3$ 의 광손상 극복 기구를 이해하기 위하여, FT-IR을 이용하여 LiNbO_3$ 단결정에 MgO 첨가와 산처리가 발생시키는 격자결함의 변화를 OH- 흡수밴드를 통하여 간접적으로 관찰하였다. 또한 액체 헬륨을 이용한 온도강하시 생기는 격자결함의 관찰과 산처리한 시편의 광택연마와 열처리에 따른 격자결함으 조사하였다. MgO 첨가는 LiNbO_3$ 격자내 $Mg_{Nb}^{2+}$ 결함을 발생시켜 광손상 저항을 증가시키며, 산처리는 결정표면의 산소층에 $H^+$이온이 침입하여 격자결함을 발생시키며, 이 격자결함은 $400^{\circ}C$이상에서 열처리하면 $H^+$가 결정내부로 확산하여 들어감을 확인하였다.

• Journal of Electrochemical Science and Technology
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• 제9권3호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2002년도 하계학술대회 논문집
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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.

• 한국분말재료학회지
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• 제13권2호
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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.