• Title/Summary/Keyword: Titanium complexes

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New Types of Constrained Geometry Catalysts Containing Silacycloalkyl Bridging Unit: Synthesis, Structure, and Polymerization Activity

  • Ok, Myung-Ahn;Hahn, Jong-Sok;Jung, Jae-Ho;Kang, Sang-Ook
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.222-222
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    • 2006
  • New types of constrained geometry complexes comprising rigid silacycloalkyl group incorporated into the bridging position between cyclopentadienyl and amido functionalities were prepared. The catalytic activities of olefin polymerization were influenced by the change of exo-cyclic ring size on bridge-head silacycloalkyl unit. It has been noted that the activities of this unique series increase with increasing size of the silacycloalkyl bridge and reach the maximum in six-membered silacyclohexyl-bridged CGC complex. It is noteworthy that conformation of silacycloalkanes gives rise to enhanced catalytic activity of the titanium center although the cyclic ring and titanium center are far remoted from each other.

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Adsorption Kinetic Study of Ruthenium Complex Dyes onto TiO2 Anodes for Dye-sensitized Solar Cells (DSSCs) (염료감응 태양전지용 루테늄 금속착체 염료의 이산화티타늄 전극에 대한 동적 흡착 연구)

  • An, Byeong-Kwan
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.24 no.11
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    • pp.929-934
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    • 2011
  • The adsorption kinetic study of ruthenium complex, N3, onto nanoporous titanium dioxide ($TiO_2$) photoanodes has been carried out by measuring dye uptake in-situ. Three simplified kinetic models including a pseudo first-order equation, pseudo second-order equation and intraparticle diffusion equation were chosen to follow the adsorption process. Kinetic parameters, rate constant, equilibrium adsorption capacities and related coefficient coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption kinetics of N3 dye molecules onto porous $TiO_2$ obeys pseudo second-order kinetics with chemisorption being the rate determining step. Additionally the heterogeneous surface and the pore size distribution of porous $TiO_2$ adsorbents were also discussed.

Development and Application of Group IV Transition Metal Oxide Precursors

  • Kim, Da Hye;Park, Bo Keun;Jeone, Dong Ju;Kim, Chang Gyoun;Son, Seung Uk;Chung, Taek-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.303.2-303.2
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    • 2014
  • The oxides of group IV transition metals such as titanium, zirconium, hafnium have many important current and future application, including protective coatings, sensors and dielectric layers in thin film electroluminescent (TFEL) devices. Recently, group IV transition metal oxide films have been intensively investigated as replacements for SiO2. Due to high permittivities (k~14-25) compared with SiO2 (k~3.9), large band-gaps, large band offsets and high thermodynamic stability on silicon. Herein, we report the synthesis of new group IV transition metal complexes as useful precursors to deposit their oxide thin films using chemical vapor deposition technique. The complexes were characterized by FT-IR, 1H NMR, 13C NMR and thermogravimetric analysis (TGA). Newly synthesised compounds show high volatility and thermal stability, so we are trying to deposit metal oxide thin films using the complexes by Atomic Layer Deposition (ALD).

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Study on the Development of CVD Precursors I-Synthesis and Properties of New Titanium β-Diketonates

  • 홍성택;임종태;이중철;Ming Xue;이익모
    • Bulletin of the Korean Chemical Society
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    • v.17 no.7
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    • pp.637-642
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    • 1996
  • Preparation and properties of potential CVD (Chemical Vapor Deposition) precursors for the TiO2, a major component of the perovskite materials such as PT, PLT, PZT, and PLZT were investigated. Reactions between β-diketones and TiMe3, formed in situ failed to produce stable Ti(β-diketonate)3 complexes but a stable purple solid, characterized as (OTi(BPP)2)2 (BPP=1,3-biphenyl-1,3-propanedione) was obtained when BPP was used. Several new Ti(Oi-Pr)2(β-diketonate)2 complexes with aromatic or ring substituents were synthesized by the substitution reaction of Ti(OiPr)4by β-diketones and characterized with 1H NMR, IR, ICP, and TGA. Solid complexes such as Ti(Oi-Pr)2(BAC)2 (BAC=1.-phenyl-2,4-pentanedione), Ti(Oi-Pr)2(BPP)2, Ti(Oi-Pr)2(1-HAN)2 (1-HAN=2-hydroxy-1-acetonaphthone), Ti(Oi-Pr)2(2-HAN)2 (2-HAN=1-hydroxy-2-acetonaphthone), Ti(Oi-Pr)2(ACCP)2 (ACCP=2-acetylcyclopentanone), and Ti(Oi-Pr)2(HBP)2 (HBP=2-hydroxybenzophenone) were found to be stable toward moisture and air. Ti(Oi-Pr)2(ACCP)2 and Ti(Oi-Pr)2(HBP)2 were proved to have lower melting points and higher decomposition temperatures. However, these complexes are thermally stable and pyrolysis under an inert atmosphere resulted in incomplete decomposition. Ti(Oi-Pr)2(DPM)2 (DPM=dipivaloylmethane) and Ti(Oi-Pr)2(HFAA)2 (HFAA=hexafluoroacetylacetone) were sublimed substantially during the thermal decomposition. Pyrolysis mechanism of these complexes are dependent on type of β-diketone but removal of Oi-Pr ligands occurs before the decomposition of β-diketonate ligands.

Photo-catalytic Oxidation of Cyanide Complexes Associated with Heavy Metals Using UV LED and Pt-dopped TiO2 (자외선 LED와 백금으로 박막된 TiO2 광촉매를 이용한 중금속과 결합한 시안화합물의 광촉매 산화)

  • Seol, Jeong Woo;Kim, Seong Hee;Lee, Woo Chun;Cho, Hyen Goo;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.28 no.1
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    • pp.29-38
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    • 2015
  • Cyanide can be leached out from the cyanidation method which has been used to extract high-purity gold and silver from ores, and it becomes a variety of cyanide complexes associated with heavy metals contained in ores. Such cyanide complexes are considered as persistent and non-degradable pollutants which cause adverse effects on humans and surrounding environments. Based on binding force between heavy metals and cyanide, cyanide complexes can be categorized weak acid dissociable (WAD) and strong acid dissociable (SAD). This study comparatively evaluated the performance of photo-catalytic process with regard to forms of cyanide complexes. In particular, both effects of UV LED wavelength and surface modification of photo-catalyst on the removal efficiency of cyanide complexes were investigated in detail. The results indicate that the performance of photo-catalytic oxidation is significantly affected by the form of cyanide complexes. In addition, the effect of UV LED wavelength on the removal efficiency was quite different between free cyanide and cyanide complexes associated with heavy metals. The results support that the surface modification of photo-catalyst, such as doping can improve overall performance of photo-catalytic oxidation of cyanide complexes.

Photo-catalytic Activity of CNT-TiO2 Nano Complex Prepared from Titanium Oxysulfate and Carbon Nanotube by Hydrosis (황산티타늄과 탄소나노튜브로부터 가수분해로 제조된 CNT-TiO2 나노복합체의 광촉매활성)

  • Kim, Sang Jin;Jung, Min-Jung;Lee, Young-Seak
    • Applied Chemistry for Engineering
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    • v.21 no.1
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    • pp.58-62
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    • 2010
  • CNT-$TiO_{2}$ nano complexes were prepared from $TiOSO_4$ and multi-walled carbon nanotube (MWCNT) by hydrolysis. The CNTs were dispersed uniformly with anatase $TiO_{2}$ in the prepared $TiO_{2}$-CNT complexes. The increasing MWCNT ratio leads to increased crystalline carbon and O/Ti ratio. The decomposition degree of methylene blue was experienced according to UV radiation time for study adsorption and photocatalytic activity. The samples having high MWCNT ratio show high adsorption and photodegradation. The high specific surface area, functional group having oxygen, low band gap energy, high electric conductivity, high volume to surface ratio, uniform structure and properties of MWCNT assist photocatalytic activity of CNT-$TiO_{2}$ complex.

Effects of enamel matrix derivative and titanium on the proliferation and differentiation of osteoblasts (법랑기질유도체를 도포한 타이태늄 표면에서 조골세포의 증식 및 분화)

  • Park, Sang-Hyun;Lee, In-Kyeong;Yang, Seung-Min;Shin, Seung-Yun;Lee, Yong-Moo;Ku, Young;Rhyu, In-Chul;Chung, Chong-Pyoung;Han, Soo-Boo;Choi, Sang-Mook
    • Journal of Periodontal and Implant Science
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    • v.33 no.3
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    • pp.359-372
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    • 2003
  • Among objectives of periodontal therapy. the principal one is the morphological and functional reconstruction of lost periodontal supporting tissues. This includes de novo formation of connective tissue attachment and the regrowth of alveolar bone. The use of enamel matrix derivative(EMD) may be a suitable means of regeneration new periodontal attachment in the infrabony defects. Implant used to replace lost tooth but, implantitis occurred after installation. The purpose of this study was to investigate the effects of EMD on differentiation and growth of osteoblast in titanium disc. Twentyfive millimeter diameter and 1mm thick Ti disc which was coated 25, 50, 100, 200${\mu}g$/ml of EMD(Emdogain(R)) used as experimental group, 25, 50, 100, 200ng/d of rhBMP-2 as positive control group, and no coat as negative control group. A human osteosarcoma cell line Saos-2 was cultured in Ti disc and cell proliferation and Alkaline phosphatase (ALP) activity were measured at 1 and 6 days. PCR was performed at 2 and 8 hours. Semi-quantitative RT-PCR for mRNA expressions of various osteoblastic differentiation markers -type I collagen, ALP, osteopontin, and bone sialoprotein - were performed at appropriate concentrations based upon the results of MTT and ALP assay. Cultured cell-disc complexes were prepared for scanning electron microscopy (SEM) at 2 hour. Data were analyzed using Mann-Whitney and repeated- measures 1-way analysis of variance(SPSS software version 10,SPSS. Chicago. IL). After culture, there was more osteoblast in EMD100${\mu}g$/ml than in EMD50, 200${\mu}g$/ml on day 6. There was significant difference in experimental and positive control group compared control group, as times go by(1 and 6 days). Alkaline phosphatase activity was different significantly in EMD100, 200${\mu}g$/ml and BMP100, 200${\mu}g$/ml on day 6. The results of reverse transcriptase-polymerase chain reaction (RT-PCR) showed that expression of mRNA for ALPase, collagen type I, osteopontin. hone sialoprotein and BMP-2 was detected at 2 hour and 8 hour in EMI 200${\mu}g$/ml subgroup and BMP100ng/ml subgroup. The results of this study suggest that application of enamel matrix derivative on osteoblast attached to titanium surface facilitate the expression of bone specific protein and the differentiation and growth of osteoblast.

Fabrication and Characterization of Dye-sensitized Solar Cells based on Anodic Titanium Oxide Nanotube Arrays Sensitized with Heteroleptic Ruthenium Dyes

  • Shen, Chien-Hung;Chang, Yu-Cheng;Wu, Po-Ting;Diau, Eric Wei-Guang
    • Rapid Communication in Photoscience
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    • v.3 no.1
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    • pp.16-19
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    • 2014
  • Anodic self-organized titania nanotube (TNT) arrays have a great potential as efficient electron-transport materials for dye-sensitized solar cells (DSSC). Herewith we report the photovoltaic and kinetic investigations for a series of heteroleptic ruthenium complexes (RD16-RD18) sensitized on TNT films for DSSC applications. We found that the RD16 device had an enhanced short-circuit current density ($J_{SC}/mAcm^{-2}=15.0$) and an efficiency of power conversion (${\eta}=7.2%$) greater than that of a N719 device (${\eta}=7.1%$) due to the increasing light-harvesting and the broadened spectral features with thiophene-based ligands. However, the device made of RD17 (adding one more hexyl chain) showed smaller $J_{SC}(14.1mAcm^{-2})$ and poorer ${\eta}(6.8%)$ compare to those of RD16 due to smaller amount of dye-loading and less efficient electron injection for the RD17 device than for the RD16 device. For the RD18 dye (adding one more thiophene unit and one more hexyl chain), we found that the device showed even lower $J_{SC}(13.2mAcm^{-2}) $ that led to a poorest device performance (${\eta}=6.2%$) for the RD18 device. These results are against to those obtained from the same dyes sensitized on $TiO_2$ nanoparticle films and they can be rationalized according to the electron transport kinetics measured using the methods of charge extraction and transient photovoltage decays.

Preparation of Dinuclear, Constrained Geometry Zirconium Complexes with Polymethylene Bridges and an Investigation of Their Polymerization Behavior

  • Noh, Seok-Kyun;Jiang, Wen-Long
    • Macromolecular Research
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    • v.12 no.1
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    • pp.100-106
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    • 2004
  • We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)[Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)]$_2$[(CH$_2$)$\_$n/][n=6(9), n=12(10)]by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear catalysts.