• Title/Summary/Keyword: transition metal

Search Result 1,203, Processing Time 0.027 seconds

Kinetic Study on Nucleophilic Substitution Reaction of 5-Nitro-8-quinolyl Benzoate, Picolinate, Nicotinate and Isonicotinate with Alkali Metal Ethoxide: Effect of Nonleaving Group on Reactivity and Transition State Structure

  • Lee, Jieun;Kim, Min-Young;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • v.35 no.6
    • /
    • pp.1789-1793
    • /
    • 2014
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of 5-nitro-8-quinolyl nicotinate (4) and 5-nitro-8-quinolyl isonicotinate (5) with alkali metal ethoxides (EtOM; M = K, Na and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOM] curve slightly upward for the reactions with EtOK and EtONa but are linear for the reactions with EtOLi and for those with EtOK in the presence of 18-crown-6-ether. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $EtO^-{\approx}EtOLi$ < EtOK < EtONa for the reactions of 4 and EtOLi < $EtO^-$ < EtOK < EtONa for the reactions of 5. Comparison of the kinetic results for the reactions of 4 and 5 with those reported previously for the corresponding reactions of 5-nitro-8-quinolyl benzoate (2) and picolinate (3) has revealed that the esters possessing a pyridine ring (i.e., 3-5) are significantly more reactive than the benzoate ester 2 due to the presence of the electronegative N atom (e.g., 2 << 3 < 4 < 5). It has been concluded that $M^+$ ion catalyzes the reactions of 3-5 by increasing the electrophilicity of the reaction center through a five-membered cyclic transition state (TS) for the reaction of 3 and via a four-membered cyclic TS for the reactions of 4 and 5.

Transition Metal Oxide Multi-Layer Color Glass for Building Integrated Photovoltaic System (BIPV 시스템을 위한 전이금속 산화물 다중층 컬러 유리 구현 기술 연구)

  • Ahn, Hyeon-Sik;Gasonoo, Akpeko;Jang, Eun-Jeong;Kim, Min-Hoi;Lee, Jae-Hyun;Choi, Yoonseuk
    • Journal of IKEEE
    • /
    • v.23 no.4
    • /
    • pp.1128-1133
    • /
    • 2019
  • This paper proposed colored front panel glass for Building Integrated Photovoltaic (BIPV) systems using multi-layered thin films composed of transition metal oxide (TMO) layers. Molybdenum oxide (MoO3) and tungsten oxide (WO3) provided complementary and suitable materials in making effective interference of reflected light from interfaces with significant difference in refractive indices. A simple, fast, and cheap fabrication method was achieved by depositing the multi-layer films in a single thermal evaporator. Magenta colored glass with optical transmittance of more than 90% was achieved with MoO3 (60nm)/WO3(100nm) multi-layered film. This technology could play in a critical role in commercial BIPV system applications.

Synthesis and Characterization of Large-Area and Highly Crystalline Molybdenum Disulphide Atomic Layer by Chemical Vapor Deposition

  • Park, Seung-Ho;Kim, Yooseok;Kim, Ji Sun;Lee, Su-Il;Cha, Myoung-Jun;Park, Chong-Yun
    • Proceedings of the Korean Vacuum Society Conference
    • /
    • 2014.02a
    • /
    • pp.356.1-356.1
    • /
    • 2014
  • The Isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. in particular, the two-dimensional layer of molybdenum disulfide (MoS2) has recently attracted much interest due to its direct-gap property and potential application in optoelectronics and energy harvesting. However, the synthetic approach to obtain high-quality and large-area MoS2 atomic thin layers is still rare. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-MoOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of mono-, bi-, and few-layered MoS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layer, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This synthetic approach is simple, scalable, and applicable to other transition metal dichalcogenides. Meanwhile, the obtained MoS2 films are transferable to arbitrary substrates, providing great opportunities to make layered composites by stacking various atomically thin layers.

  • PDF

Synthesis of Tridentate Poly-amine Ligands and Determination of Stability Constants of Transition Metal Complexes (세자리 폴리아민리간드의 합성과 양성자 해리상수 및 전이금속과의 착물 안정도상수의 결정)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Ko, Moon-Soo
    • Analytical Science and Technology
    • /
    • v.15 no.2
    • /
    • pp.135-141
    • /
    • 2002
  • The new tridentate poly-amine ligands, N,N-Bis(2-amino-ethyl)-methyl amine${\cdot}$2HBr (BAMA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-ethylamine${\cdot}$2HBr (BAEA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-propylamine${\cdot}$2HBr (BAPA${\cdot}$2HBr) and N,N-Bis(2-amino-ethyl)-butylamine${\cdot}$2HBr (BABA${\cdot}$2HBr) were synthesized as their dihydrobromic-salt and characterized by EA, IR, NMR and Mass spectroscopy. The protonation constants of the ligands and stability constants of transition metal(II) complexes were determined in aqueous solutions by potentiometry and compared with diethylenetriamine. Stability constants for transition metal complexes of ligands are in the order of BAMA < BAEA < BAPA > BABA. The larger value of stability constants of BAPA compared to these BABA, may be attributed to the more distorted structure of the complex due to the increased steric crowding caused by the presence of the bulky N-butyl group.

A Series of Transition-metal Coordination Complexes Assembled from 3-Nitrophthalic Acid and Thiabendazole: Synthesis, Structure and Properties

  • Xu, Wen-Jia;Xue, Qi-Jun;Liang, Peng;Zhang, Ling-Yu;Huang, Yan-Feng;Feng, Yu
    • Bulletin of the Korean Chemical Society
    • /
    • v.35 no.1
    • /
    • pp.218-224
    • /
    • 2014
  • In order to explore new coordination frameworks with novel designed 3-nitrophthalic acid and the same N-donor ancillary ligand, a series of novel coordination complexes, namely, $[Cd_2(3-NPA)_2(TBZ)_2(H_2O)_2]{\cdot}2H_2O$(1), $[Zn_2(3-NPA)_2(TBZ)_2]$(2), $[Zn_2O(3-NPA)(TBZ)(H_2O)]_n$(3), $[Co(3-NPA)(TBZ)(H_2O)]_n$(4) (3-$NPAH_2$ = 3-nitrophthalic acid), have been hydrothermally synthesized through the reaction of 3-nitrophthalic acid with divalent transition-metal salts in the presence of N-donor ancillary coligand (TBZ = thiabendazole). As a result of various coordination modes of the versatile 3-$NPAH_2$ and the coligand TBZ, these complexes exhibit structural diversity. X-ray structure analysis reveals that 1 and 2 are 0D molecular rings, while 3 and 4 are one-dimensional (1D) infinite chain polymers. And the weak O-H${\cdots}$O hydrogen bonds and C-H${\cdots}$O nonclassical hydrogen bonds as well as ${\pi}-{\pi}$ stacking also play important roles in affecting the final structure where complexes 1, 3 and 4 have 3D supramolecular architectures, while complex 2 has a 2D supramolecular network. Also, IR spectra, fluorescence properties and thermal decomposition process of complexes 1-4 were investigated.

Complex Formation of 1,15-Diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane with Some Transition Metal Ions (전이금속이온과 1,15-Diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane과의 착물형성)

  • Cheul-Gyu Chang;Young-Kook Shin;Si-Joong Kim
    • Journal of the Korean Chemical Society
    • /
    • v.30 no.6
    • /
    • pp.526-531
    • /
    • 1986
  • The stability constants of 1,15-diaza-3,4:12,13-dibenzo-5,8,11-trioxacycloheptadecane (NenOdien H$_4$, L) with transition metal ions such as $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ have been determined by potentiometry in 95% methanol solution at 25$^{\circ}$C. The complex formation of the NenOdien $_4$ with the transition metal ions depends on the basicity of the donor atoms. The order of complex stability was Co(II) < Ni(II) < Cu(II) > Zn(II). The geometries of the complexes in solid state were discussed by visible-near infrared and infrared spectrophotometry, elemental analysis and electro-conductivity. The results suggest that the geometries of the solid complexes are octahedral for $[CoL_2(OH_2)Cl]Cl{\cdot}2H_2O$, $[NiL_2(OH_2)Cl]Cl{\cdot}2H_2O$, and $[ZnLCl_2]{\cdot}\frac{1}{2}H_2O$ and square pyramidal for [CuLCl]Cl, respectively.

  • PDF

Effect of Alkali Metal Ions on Alkaline Ethanolysis of 2-Pyridyl and 4-Pyridyl Benzoates in Anhydrous Ethanol

  • Lee, Jae-In;Kang, Ji-Sun;Kim, Song-I;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • v.31 no.10
    • /
    • pp.2929-2933
    • /
    • 2010
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured for nucleophilic substitution reactions of 2-pyridyl benzoate 5 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol. The plots of $k_{obsd}$ vs. $[EtOM]_o$ are curved upwardly but linear in the excess presence of 18-crown-6-ether (18C6) with significant decreased $k_{obsd}$ values in the reaction with EtOK. The $k_{obsd}$ value for the reaction of 5 with a given EtONa concentration decreases steeply upon addition of 15-crown-5-ether (15C5) to the reaction medium up to ca. [15C5]/$[EtONa]_o$ = 1, and remains nearly constant thereafter, indicating that $M^+$ ions catalyze the reaction in the absence of the complexing agents. Dissection $k_{obsd}$ into $k_{EtO^-}$- and $k_{EtOM}$, i.e., the second-order rate constants for the reaction with the dissociated $EtO^-$ and the ion-paired EtOM, respectively has revealed that ion-paired EtOM is 3.2 - 4.6 times more reactive than dissociated $EtO^-$. It has been concluded that $M^+$ ions increase the electrophilicity of the reaction center through a 6-membered cyclic transition state. This idea has been examined from the corresponding reactions of 4-pyridyl benzoate 6, which cannot form such a 6-membered cyclic transition state.

Characteristics of methane reforming with carbon dioxide using transition metal catalyts (전이금속 촉매를 이용한 이산화탄소와 메탄의 개질 특성)

  • Jang, Hyun Tae
    • Journal of the Korea Academia-Industrial cooperation Society
    • /
    • v.22 no.2
    • /
    • pp.644-650
    • /
    • 2021
  • This study characterized the reforming of methane with carbon dioxide, which is a major cause of global warming. The methane decomposition reaction with carbon dioxide was carried out using transition metal catalysts. The reactivity of tin was lower than that of a transition metal, such as nickel and iron. Most of the decomposition reaction occurred in the solid state. The melting point of tin is 505.03 K. Tin reacts in a liquid phase at the reaction temperature and has the advantage of separating carbon produced by the decomposition of methane from the liquid tin catalyst. Therefore, deactivation due to the deposition of carbon in the liquid tin can be prevented. Methane decomposition with carbon dioxide produced carbon monoxide and hydrogen. Ni was used to promote the catalyst performance and enhance the activity of the catalyst and lifetime. In this study, catalysts were synthesized using the excess wet impregnation method. The effect of the reaction temperature, space velocity was measured to calculate the activity of catalysts, such as the activation energy and regeneration of catalysts. The carbon-deposited tin catalyst regeneration temperature was 1023 K. The reactivity was improved using a nickel co-catalyst and a water supply.

Sintering Behavior and Mechanical Property of Transition Metal Carbide-Based Cermets by Spark Plasma Sintering (방전플라즈마 소결 공정 적용 전이금속 카바이드 서멧의 소결 및 기계적 특성)

  • Lee, Jeong-Han;Park, Hyun-Kuk;Hong, Sung-Kil
    • Korean Journal of Materials Research
    • /
    • v.32 no.1
    • /
    • pp.44-50
    • /
    • 2022
  • Transition metal carbides (TMCs) are used to process difficult-to-cut materials due to the trend of requiring superior wear and corrosion properties compared to those of cemented carbides used in the cutting industry. In this study, TMC (TiC, TaC, Mo2C, and NbC)-based cermets were consolidated by spark plasma sintering at 1,300 ℃ (60 ℃min) with a pressure of 60 MPa with Co addition. The sintering behavior of TMCs depended exponentially on the function of the sintering exponent. The Mo2C-6Co cermet was fully densified, with a relative density of 100.0 %. The Co-binder penetrated the hard phase (carbides) by dissolving and re-precipitating, which completely densified the material. The mechanical properties of the TMCs were determined according to their grain size and elastic modulus: TiC-6Co showed the highest hardness of 1,872.9 MPa, while NbC-6Co showed the highest fracture toughness of 10.6 MPa*m1/2. The strengthened grain boundaries due to high interfacial energy could cause a high elastic modules; therefore, TiC-6Co showed a value of 452 ± 12 GPa.

Research Trends on Interface-type Resistive Switching Characteristics in Transition Metal Oxide (전이 금속 산화물 기반 Interface-type 저항 변화 특성 향상 연구 동향)

  • Dong-eun Kim;Geonwoo Kim;Hyung Nam Kim;Hyung-Ho Park
    • Journal of the Microelectronics and Packaging Society
    • /
    • v.30 no.4
    • /
    • pp.32-43
    • /
    • 2023
  • Resistive Random Access Memory (RRAM), based on resistive switching characteristics, is emerging as a next-generation memory device capable of efficiently processing large amounts of data through its fast operation speed, simple device structure, and high-density implementation. Interface type resistive switching offer the advantage of low operation currents without the need for a forming process. Especially, for RRAM devices based on transition metal oxides, various studies are underway to enhance the memory characteristics, including precise material composition control and improving the reliability and stability of the device. In this paper, we introduce various methods, such as doping of heterogeneous elements, formation of multilayer films, chemical composition adjustment, and surface treatment to prevent degradation of interface type resistive switching properties and enhance the device characteristics. Through these approaches, we propose the feasibility of implementing high-efficient next-generation non-volatile memory devices based on improved resistive switching properties.