• Title/Summary/Keyword: Solid state synthesis

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Synthesis, Characterization and ESR Studies of New Copper(II) Complexes of Vicinal Oxime Ligands (Vicinal Oxime 리간드의 새로운 구리(II) 착물에 대한 합성, 특성 및 ESR 연구)

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
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    • v.55 no.4
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    • pp.603-611
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    • 2011
  • Ethoxylacetyl oxime ligands [HL, (1) and $H_2L^1$, (3)] react with copper(II) acetate monohydrate yield octahedral and square planar complexes, respectively. The complexes have been postulated due to elemental analyses, IR, UVVis. spectra, magnetic susceptibility, conductivity and ESR spectra. Molar conductance of the complexes in DMF indicates a non-ionic character. The ESR spectra of [$(L)_2Cu(H_2O)_2$], (2) complex at room temperature and 77K are characteristic of an axial symmetry ($d_{x2-y2}$) with covalent bond character and have a large line width typical of dipolar interactions. However, [$(L^1)Cu$], (4) complex in the solid state showed spectra of marked broadening and loss of hyperfine splitting confirming spinexchange interactions between the copper(II) sites. The spectrum of the doped copper(II) complex at room temperature showed super-hyperfine splitting from coordinated nitrogen atoms and it has an axial type ($d_{x2-y2}$) with covalent bond character and an essentially square-planar arrangement around the copper(II) ion. The spectrum of [$(L^1)Cu$], (4) in frozen methanol at 77K was characteristic of the triplet state of a dimer species and the distance found between the two copper(II) centers was calculated and is equal to 4.8 ${\AA}$.

Synthesis and luminescent properties of a new green $CaZrO_3:\;HO_{3+}$ long persistent phosphors (녹색 발광의 $CaZrO_3:\;HO_{3+}$ 축광성 형광체의 합성 및 발광 특성)

  • Park, Byeong-Seok;Choi, Jong-Keon
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.18 no.3
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    • pp.109-114
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    • 2008
  • Novel green long persistent phosphors of $CaZrO_3$ : $HO_{3+}$ have been synthesized at high temperature with weak reduction atmosphere by traditional solid state reaction method. The role of $H_3BO_3$ as flux and the suitable concentration of Ho as activator on the $CaZrO_3$ : $HO_{3+}$ long persistent phosphors has been investigated. Crystals of $HO_{3+}$ doped $CaZrO_3$ long persistent phosphores were characterized by fluorescence spectrophotometer and photoluminescence (PL). The main emission spectra of 546 nm peak was revealed through synthesizing at high temperature in $N_2$ gas atmosphere. The after glow emission spectra of $CaZrO_3$ : $HO_{3+}$ long persistent phosphores arise at 546 nm peak of narrow range. because that revealed pure green color. Green long persistent phosphors have been observed in the system for over 5 h after UV irradiation (254 nm). The main emission peak was ascribed to $HO_{3+}$ ions transition from $^5F_4$, $^5S_2{\to}^5I_3$, and the after glow may be ascribed to the trap centers in the $CaZrO_3$ host lattice.

Change of Electrochemical Characteristics Due to the Fe Doping in Lithium Manganese Oxide Electrode

  • Ju Jeh Beck;Kang Tae Young;Cho Sung Jin;Sohn Tae Won
    • Journal of the Korean Electrochemical Society
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    • v.7 no.3
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    • pp.131-137
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    • 2004
  • Sol-gel method which provides better electrochemical and physiochemical properties compared to the solid-state method was used to synthesize the material of $LiFe_yMn_{2-y}O_4$. Fe was substituted to increase the structural stability so that the effects of the substitution amount and sintering temperature were analyzed. XRD was used for the structural analysis of produced material, which in turn, showed the same cubic spinel structure as $LiMn_2O_4$ despite the substitution of $Fe^{3+}$. During the synthesis of $LiFe_yMn_{2-y}O_4$, as the sintering temperature and the doping amount of Fe(y=0.05, 0.1, 0.2)were increased, grain growth proceeded which in turn, showed a high crystalline and a large grain size, certain morphology with narrow specific surface area and large pore volume distribution was observed. In order to examine the ability for the practical use of the battery, charge-discharge tests were undertaken. When the substitution amount of $Fe^{3+}\;into\;LiMn_2O_4$ increased, the initial discharge capacity showed a tendency to decrease within the region of $3.0\~4.2V$ but when charge-discharge processes were repeated, other capacity maintenance properties turned out to be outstanding. In addition, when the sintering temperature was $800\~850^{\circ}C$, the initial capacity was small but showed very stable cycle performance. According to EVS(electrochemical voltage spectroscopy) test, $LiFe_yMn_{2-y}O_4(y=0,\;0.05,\;0.1,\;0.2)$ showed two plateau region and the typical peaks of manganese spinel structure when the substitution amount of $Fe^{3+}$ increased, the peak value at about 4.15V during the charge-discharge process showed a tendency to decrease. From the previous results, the local distortion due to the biphase within the region near 4.15V during the lithium extraction gave a phase transition to a more suitable single phase. When the transition was derived, the discharge capacity decreased. However the cycle performance showed an outstanding result.

Synthesis of Porous $TiO_2$ Thin Films Using PVC-g-PSSA Graft Copolymer and Their Use in Dye-sensitized Solar Cells (PVC-g-PSSA 가지형 공중합체를 이용한 다공성 $TiO_2$ 박막의 합성 및 염료감응 태양전지 응용)

  • Byun, Su-Jin;Seo, Jin-Ah;Chi, Won-Seok;Shul, Yong-Gun;Kim, Jong-Hak
    • Membrane Journal
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    • v.21 no.2
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    • pp.193-200
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    • 2011
  • An amphiphilic graft copolymer comprising a poly(vinyl chloride) (PVC) backbone and poly (styrene sulfonic acid) (PSSA) side chains (PVC-g-PSSA) was synthesized via atom transfer radical polymerization (ATRP). Mesoporous titanium dioxide $(TiO_2)$ films with crystalline anatase phase were synthesized via a sol-gel process by templating PVC-g-PSSA graft copolymer. Titanium isopropoxide (TTIP), a $TiO_2$ precursor was selectively incorporated into the hydrophilic PSSA domains of the graft copolymer and grew to form mesoporous $TiO_2$ films, as confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The performances of dye-sensitized solar cell (DSSC) were systematically investigated by varying spin coating times and the amounts of P25 nanoparticies. The energy conversion efficiency reached up to 2.7% at 100 mW/$cm^2$ upon using quasi-solid-state polymer electrolyte.

Photovoltaic Properties of Dendritic Photosensitizers containing multi-chromophore for Dye-sensitized Solar Cells (multi-chromophore를 가지는 유기염료의 DSSC 광전변환거동)

  • Kim, MyeongSeok;Cheon, Jong Hun;Jung, DaeYoung;Kim, JaeHong
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.117.2-117.2
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    • 2011
  • Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline TiO2 electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline TiO2. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

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Synthesis of $Fe/Al_2O_3$ and $Fe/TiO_2$ nanocomposite powder by mechanical alloying (기계적합금화에 의한 $Fe/Al_2O_3$$Fe/TiO_2$계 나노복합분말의 제조)

  • Lee, Seong-Hee;Lee, Chung-Hyo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.19 no.4
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    • pp.202-207
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    • 2009
  • Nanocomposite formation of metal-metal oxide systems by mechanical alloying (MA) has been investigated at room temperature. The systems we chose are the $Fe_3O_4$-M (M = AI, Ti), where pure metals are used as reducing agent. It is found that $Fe/Al_2O_3$ and $Fe/TiO_2$ nanocomposite powders in which $Al_2O_3$ and $TiO_2$ are dispersed in ${\alpha}$-Fe matrix with nano-sized grains are obtained by MA of $Fe_3O_4$ with Al and Ti for 25 and 75 hours, respectively. It is suggested that the shorter MA time for the nanocomposite formation in $Fe/Al_2O_3$ is due to a large negative heat associated with the chemical reduction of magnetite by aluminum. X-ray diffraction results show that the average grain size of ${\alpha}$-Fe in $Fe/TiO_2$ nanocomposite powders is in the range of 30 nm. The change in magnetic properties also reflects the details of the solid-state reduction of magnetite by pure metals during MA.

A Study on the Synthesis and the Electrochemical Properties of $LiNi_{1-y}$${Co_y}{O_2}$from $Li_2$$CO_3$, ${NiCO_3}$, and $CoCO_3$ ($Li_2$$CO_3$, ${NiCO_3}$, $CoCO_3$로부터 $LiNi_{1-y}$${Co_y}{O_2}$의 합성 및 전극특성 연구)

  • Rim, Ho;Kang, Seong-Gu;Chang, Soon-Ho;Song, Myoung-Youp
    • Journal of the Korean Ceramic Society
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    • v.38 no.6
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    • pp.515-521
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    • 2001
  • 출발 물질로서 L $i_2$C $O_3$, NiC $O_3$, CoC $O_3$를 사용하고 조성과 합성 온도를 변화시켜, 고온 고상법에 의하여 LiN $i_{1-y}$ $Co_{y}$ $O_2$(y=0.1, 0.3, 0.5)를 합성하였다. 합성과 시료들의 결정구조, 미세구조 그리고 전기화학적 특성을 조사하였다. 80$0^{\circ}C$와 8$50^{\circ}C$에서 제조한 L $i_{x}$N $i_{1-y}$ $Co_{y}$ $O_2$는, 삼방정계(space group: R3m)의 $\alpha$-NaFe $O_2$구조로 결정화되어 있는 층상 구조를 형성하였다. LiN $i_{1-y}$ $Co_{y}$ $O_2$(y=0.1, 0.3, 0.5)는 Co의 양이 증가함에 따라 a축과 c축의 크기가 감소하였는데, 이는 코발트 이온의 크기가 니켈 이온의 크기보다 작은데 기인하는 것이다. 그러나 c축과 a축의 크기의 비(c/a)가 증가하였음은 이차원적 구조가 잘 발달됨을 보여준다. 니켈에 대한 코발트의 치환량에 따른 리튬 이온의 삽입/추출 가역성은 코발트의 치환량이 증가하면서 증가하여 y=0.3인 LiN $i_{0.9}$ $Co_{0.1}$ $O_2$에서 대체로 우수하였고 그 이상으로 y값이 증가하면 가역성이 나빠졌다. 80$0^{\circ}C$에서 합성한 LiN $i_{0.9}$ $Co_{0.1}$ $O_2$가 가장 큰 초기 방전 용량 146 mAh/g을 나타내었으며, 싸이클링 성능도 비교적 우수하였다. 8$50^{\circ}C$에서 합성한 LiN $i_{0.9}$ $Co_{0.1}$ $O_2$와 LiN $i_{0.7}$ $Co_{0.3}$ $O_2$가 우수한 싸이클링 성능을 보였다.다. 싸이클링 성능을 보였다.다.보였다.다.

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Synthesis of Zn2SiO4 : Mn Phosphor Particles by Spray-pyrolysis Method (분무 열 분해법을 이용한 Zn2SiO4 : Mn 나노 형광체의 광학적 특성에 관한 연구)

  • Nam, Sang-Hun;Kim, Myoung-Hwa;Lee, Sang-Duck;Boo, Jin-Hyo
    • Journal of the Korean Vacuum Society
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    • v.19 no.1
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    • pp.66-71
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    • 2010
  • Spherical shape $Zn_2SiO_4:Mn$ phosphor particles with the mean particle size from submicron to micron sizes were prepared by ultrasonic spray pyrolysis method. A droplet separator was introduced to control the size distribution of the phosphor particles with spherical shape. The $Zn_2SiO_4:Mn$ phosphor particles with 2 mol% doping concentration of manganese have decay time and have photoluminescence intensities comparable with those of the latest commercial product prepared by the solid state reaction method. The size of the phosphor particles was decreased from 1 to 0.2 micrometers as the inorganic salt solution concentration was changed from 0 to 5 M. The phosphor particles prepared from the solutions above 0.5 M have photoluminescence intensities comparable with that of the latest commercial product.

Synthesis of Chromium Nitride and Evaluation of its Catalytic Property (크롬 질화물(CrN)의 합성 및 촉매특성에 관한 연구)

  • Lee, Yong-Jin;Kwon, Heock-Hoi
    • Applied Chemistry for Engineering
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    • v.17 no.5
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    • pp.451-457
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    • 2006
  • We synthesized phase pure CrN having surface areas up to $47m^2/g$ starting from $CrCl_{3}$ with $NH_{3}$. Thermal Gravimetric Analysis coupled with X-ray diffraction was carried out to identify solid state transition temperatures and the phase after each transition. In addition, the BET surface areas, pore size distributions, and crystalline diameters for the synthesized materials were analyzed. Space velocity influenced a little to the surface areas of the prepared materials, while heating rate did not. We believe it is due to the fast removal of reaction by-products from the system. Temperature programmed reduction results revealed that the CrN was hardly passivated by 1% $O_{2}$. Molecular nitrogen was detected from CrN at 700 and $950^{\circ}C$, which may be from lattice nitrogen. In temperature programmed oxidation with heating rate of 10 K/min in flowing air, oxidation started at or higher than $300^{\circ}C$ and resulting $Cr_{2}O_{3}$ phase was observed with XRD at around $800^{\circ}C$. However the oxidation was not completed even at $900^{\circ}C$. CrN catalysts were highly active for n-butane dehydrogenation reaction. Their activity is even higher than that of a commercial $Pt-Sn/Al_{2}O_{3}$ dehydrogenation catalyst in terms of volumetric reaction rate. However, CrN was not active in pyridine hydrodenitrogenation.

Synthesis, Potentiometric, Spectral Characterization and Microbial Studies of Transition Metal Complexes with Tridentate Ligand (세자리 리간드의 전이금속 착물에 대한 합성과 전위차 및 분광학적 확인 그리고 미생물학적 연구)

  • Jadhav, S.M.;Munde, A.S.;Shankarwar, S.G.;Patharkar, V.R.;Shelke, V.A.;Chondhekar, T.K.
    • Journal of the Korean Chemical Society
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    • v.54 no.5
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    • pp.515-522
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    • 2010
  • A relation between antimicrobial activities and the formation constants of solid complexes of Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with tridentate Schiff base ligand, 4-hydroxy-3(1-{2-(benzylideneamino)-phenylimino}-ethyl)-6-methyl-2Hpyran-2-one (HL) derived from o-phenylene diamines, dehydroacetic acid (DHA) and p-chloro benzaldehyde have been studied. The ligand and metal complexes were characterized by elemental analysis, conductivity, magnetic susceptibility, thermal analysis, X-ray diffraction, IR, $^1H$-NMR, UV-vis and mass spectra. From the analytical data, the stiochiometry of the complexes was found to be 1:2 (metal:ligand) with octahedral geometry. The molar conductance values suggest the nonelectrolytic nature of metal complexes. The X-ray diffraction data suggests monoclinic crystal system for Ni(II) and orthorhombic crystal system for Cu(II) and Co(II) complexes. The IR spectral data suggest that the ligand behaves as tridentate ligand with ONN donor atoms sequence towards central metal ion. Thermal behavior (TG/DTA) and kinetic parameters calculated by Coats-Redfern method suggests more ordered activated state in complex formation. The protonation constants of the complexes were determined potentiometrically in THF:water (60:40) medium at $25^{\circ}C$ and ionic strength ${\mu}=0.1\;M$ ($NaClO_4$). Antibacterial activities in vitro were performed against Staphylococcus aureu and Escherichia coli. Antifungal activities were studied against Aspergillus Niger and Trichoderma. The effect of the metal ions and stabilities of complexes on antimicrobial activities are discussed.