• 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.

• Journal of Magnetics
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• 제13권2호
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• pp.61-64
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• 2008

We studied the effect of the variation of the lattice constant on the electrical properties of $SrRuO_3$ thin films. In order to obtain films with different volumes, we varied the substrate temperature and oxygen pressure during the growth of the films on $SrTiO_3$ (001) substrates. The films were grown using a pulsed laser deposition method. The X-ray diffraction patterns of the grown films at low temperature and low oxygen pressure indicated the elongation of the c-axis lattice constant compared to that of the films grown at a higher temperature and higher oxygen pressure. The in-plane strain states are maintained for all of the films, implying the expansion of the unit-cell volume by the oxygen vacancies. The variation of the electrical resistance reflects the temperature dependence of the resistivity of the metal, with a ferromagnetic transition temperature inferred form the cusp of the curve being observed in the range from 110 K to 150 K. As the c-axis lattice constant decreases, the transition temperature linearly increases.

• Bulletin of the Korean Chemical Society
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• 제5권1호
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• pp.41-44
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• 1984

The oxidation of carbon monoxide has been investigated on Ni-doped ${\alpha}-Fe_2O_3$ catalyst at 300 to $450^{\circ}$. The oxidation rates have been correlated with 1.5-order kinetics; first with respect to CO and 1/2 with respect to $O_2$. Carbon monoxide is adsorbed on lattice oxygen of Ni-doped ${\alpha}-Fe_2O_3$, while oxygen appears to be adsorbed on oxygen vacancy formed by Ni-doping. The conductivities show that adsorption of CO on O-lattice produces conduction electron and adsorption of $O_2$ on O-vacancy withdraws the conduction electron from vacancy. The adsorption process of CO on O-lattice is rate-determining step and dominant defect of Ni-doped ${\alpha}-Fe_2O_3$ is suggested from the agreement between kinetic and conductivity data.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.359-360
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• 2013

The effect of electrode and deposition methods on non-linear interfacial resistive switching in HfO2 based $250{\times}250$ nm2 cross-point device was studied. HfO2 based device has the interfacial resistive switching properties of non-linearity and self-compliance current switching. The operating current in HfO2 based device was increased with negatively increasing the heat of formation energy in top electrode. Also, it was investigated that the operating current in HfO2 based device was changed with deposition methods of O3 reactant ALD, H2O reactant ALD and dc reactive sputtering, resulting the magnitude of the operating current and on/off ratio in order of HfO2 films deposited by dc reactive sputtering, H2O reactant ALD, and O3 reactant ALD. To investigate the effect of electrode and deposition methods on operating current of non-linear interfacial resistive switching in the cross-point device, X-ray photoelectron spectroscopy was measured. Through the analysis of O 1s spectra, non-lattice oxygen concentration, which is closely related to oxygen vacancies, was increased in order of Pt, TiN, and Ti top electrodes and in order of O3 reactant ALD, H2O reactant ALD, and O3 reactant ALD, and dc reactive sputtering deposition method. From all results, non-lattice oxygen concentration in ultra-thin HfO2 films play a crucial role in the operating current and memory states (LRS & HRS) in the non-linear interfacial resistive switching.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.378.1-378.1
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• 2014

In this study, we investigated that the resistance switching characteristics of Nb-doped HfO2 films with increasing Nb doping concentration. The Nb-doped HfO2 based ReRAM devices with a TiN/Nb-doped HfO2/Pt/Ti/SiO2 were fabricated on Si substrates. The Nb-doped HfO2 films were deposited by reactive dc magnetron co-sputtering at $300^{\circ}C$ and oxygen partial ratio of 60% (Ar: 16sccm, O2: 24sccm). Microstructure of Nb-doped HfO2 films and atomic concentration were investigated by XRD, TEM, and XPS, respectively. The Nb-doped HfO2 films showed set/reset resistance switching behavior at various Nb doping concentrations. The process voltage of forming/set is decreased and whereas the initial current level is increased in doped HfO2 films. However, the switching properties of Nb-doped HfO2 were changed above the specific doping concentration of Nb. The change of resistance switching behavior depending on doping concentration was discussed in terms of concentration of non-lattice oxygen and micro-structure of Nb-doped HfO2.

• 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.

• 공업화학
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• 제23권1호
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• pp.119-123
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• 2012

본 연구는 Mn/$TiO_2$ 촉매를 이용한 저온 $NH_3$-SCR 반응에서 산소의 역할에 대한 영향을 기술하였다. 촉매의 격자산소는 저온 SCR 반응에 참여하며, 기상의 산소는 환원된 촉매를 재산화 시키는 역할을 한다. 이러한 산소의 redox 특성은 SCR 반응활성에 중요한 요소로 작용하며, 격자산소의 이용능력은 표면에 노출된 망간의 산화상태에 큰 영향을 받는다. $TiO_2$ 담체 표면에 존재하는 Mn이 $MnO_2$의 망간산화물 형태로 존재할 때가 $Mn_2O_3$의 형태로 존재할 때보다 우수한 redox 특성을 가지며, 이러한 망간의 산화상태는 $TiO_2$의 비표면적에 큰 영향을 받는다.

• 공업화학
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• 제27권2호
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• pp.128-134
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• 2016

최근 셰일가스의 개발로 프로판, 부탄과 같은 경질알칸으로부터 프로필렌, 부텐, 부타디엔과 같은 올레핀을 제조하는 탈수소 공정에 대한 연구와 상용화가 많이 진행되었다. 특히 직접 탈수소화 반응의 열역학적 한계를 극복하고자 산화적 탈수소 또는 선택적 수소 산화 반응과 같이 산소를 활용한 기술의 연구개발이 진행되거나, 실제 공정에 적용된 사례들도 보고되고 있다. 이에 본 연구에서는 경질알칸의 탈수소 반응을 위한 산소활용기술의 최근 연구동향을 가스상의 산소를 활용하는 방법과 고체산화물의 격자산소를 활용한 기술로 나누어 정리하고, 산소활용기술의 현황과 연구 개발 방향 및 향후 전망에 대해 고찰하였다. 반응물의 반응성에 따라 기체상 산소의 적용이 용이한 경우와 반응성의 조절을 위해 격자산소를 이용하는 기술로 분류할 수 있었고, 전환율을 높이면서 선택도를 낮추지 않는 기술의 개발이 주요한 목표가 되었다.

• The Korean Journal of Ceramics
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• 제4권2호
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• pp.128-135
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• 1998

The paper gives a brief introduction to protonic defects and their chemistry, thermodynamics and transport in oxides. The temperature dependence of the equilibrium concentration of protons is illustrated and compared for different acceptor-doped oxides. The difficulties of saturating as well as emptying the oxides of protons are discussed. In order to illustrate the possibility of lattice relaxation of defects, a conceptual study is made of a case where the enthalpy of dissolution of protons(water) at the cost of oxygen vacancies is assumed dependent on the concentration of vacancies. It is shown how this changes the behavior of hydration curves vs temperature and water vapour pressure. finally, a discussion is given on the water uptake in heavily oxygen deficient oxides; how water uptake may affect order-disorder in the oxygen sublattice and eventually lead to defective, disordered or ordered oxyhydroxides or hydroxides of potential interest as intermediate temperature proton conductions.