• Title/Summary/Keyword: lattice oxygen

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Lattice Oxygen Activation in NiFe (Oxy)hydroxide using Se (셀레늄을 활용한 니켈철 (옥시)수산화물의 격자 산소 활성화)

  • Jo, Seunghwan;Sohn, Jung Inn
    • 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-/O22-) 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.

The Role of Lattice Oxygen in the Selective Catalytic Reduction of NOx on V2O5/TiO2 Catalysts (V2O5/TiO2 촉매의 선택적 환원촉매반응에서 격자산소의 역할)

  • Ha, Heon-Phil;Choi, Hee-Lack
    • 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.

Electrical Properties of SrRuO3 Thin Films with Varying c-axis Lattice Constant

  • Chang, Young-J.;Kim, Jin-I;Jung, C.U.
    • Journal of Magnetics
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    • v.13 no.2
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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.

Kinetics and Mechanisms of the Oxidation of Carbon Monoxide on Ni-Doped $\alpha-Fe_2O_3$

  • Kim, Keu-Hong;Jun, Jong-Ho;Choi, Jae-Shi
    • Bulletin of the Korean Chemical Society
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    • v.5 no.1
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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.

Effect of Non-lattice Oxygen Concentration on Non-linear Interfacial Resistive Switching Characteristic in Ultra-thin HfO2 Films

  • Kim, Yeong-Jae;Kim, Jong-Gi;Mok, In-Su;Lee, Gyu-Min;Son, Hyeon-Cheol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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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.

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Effect of Non-lattice Oxygen Concentration and Micro-structure on Resistance Switching Characteristics in Nb-doped HfO2 by DC Magnetron Co-Sputtering

  • Lee, Gyu-Min;Kim, Jong-Gi;Kim, Yeong-Jae;Kim, Jong-Il;Son, Hyeon-Cheol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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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.

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Characteristics of SO2 Oxidation of Pt/TiO2 Catalyst according to the Properties of Platinum Precursor (Platinum Precursor 특성에 따른 Pt/TiO2 촉매의 SO2 산화 반응특성 연구)

  • Kim, Jae Kwan;Park, Seok Un;Nam, Ki Bok;Hong, Sung Chang
    • 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 PtClx 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.

The Effect of Oxygen in Low Temperature SCR over Mn/$TiO_2$ Catalyst (Mn/$TiO_2$ 촉매를 이용한 저온 SCR 반응에서 산소의 영향)

  • Lee, Sang Moon;Choi, Hyun Jin;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.23 no.1
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    • pp.119-123
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    • 2012
  • This study presents the effect of oxygen on the $NH_3$ selective catalytic reduction (SCR) by Mn/$TiO_2$ catalyst. The lattice oxygen of catalysts is participate in the low temperature SCR, and the gaseous oxygen directly takes part in the rexoidtion of reduced catalyst. These redox properties of oxygen an play important role in SCR activity and the available capability of lattice oxygen depends on the manganese oxidation state of the catalyst surface. $MnO_2$ species has a higher redox property than that of $Mn_2O_3$ species on deposited $TiO_2$ surface and these manganese oxide states strongly depend on the $TiO_2$ surface area.

Research Trends of Technology Using Oxygen for Dehydrogenation of Light Alkanes (경질알칸의 탈수소 반응을 위한 산소활용기술 연구 동향)

  • Koh, Hyoung Lim
    • Applied Chemistry for Engineering
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    • v.27 no.2
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    • pp.128-134
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    • 2016
  • Due to the great development made in converting the shale gas into the more valuable products, research and commercialization for production technology of olefins like propylene, butenes, butadiene from light alkanes have been intensively investigated. Especially the technology using oxygen like oxidative dehydrogenation or selective hydrogen combustion to overcome thermodynamic limit of direct dehydrogenation conversion has been extensively studied and some cases of applying this technology to the plant scale was reported. In this review, we have categorized the technology into two parts; gas phase oxygen utilization technology and lattice oxygen utilization technology. The trends, results and future direction of the technology are discussed.

Dissolution of Protons in Oxides

  • Norby, Truls
    • The Korean Journal of Ceramics
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    • v.4 no.2
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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.

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