• Title/Summary/Keyword: Lanthanide ions

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Study on CMPO (Carbamoylphosphate) derivative functionalized ordered mesoporous silicates for selective removal of lanthanide (희토류 원소의 분리를 위한 표면 개질 된 메조 다공성 실리케이트의 개발에 관한 연구)

  • Kwon, Bob Jin;Jung, Hyun;Kim, Jong Young
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.22 no.6
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    • pp.291-298
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    • 2012
  • Carbamoylphosphate (CMPO) [CMPO analogue; 2-(diphenylphosphoryl)-N-(3-(triethoxysilyl)propyl)acetamide]silane, as a functional self-assembled molecules, grafted mesoporous silicates were prepared by simple hydrolysis and condensation reaction. Pore sized tailored mesoporous silicates such as MCM-41, SBA-15, or amorphous silica nanoparticles were adopted as host materials. The surface area of ordered mesoporous silicates was ranged from 680 $m^2/g$ to 1310 $m^2/g$ with different pore diameters that estimated to be ca. 2.3~9.1 nm by BJH method. Among the OMMs host materials, SBA-15(II) has higher loading ratio (~35 wt%) of CMPO derivative than other OMMs. Accessibility to CMPO silane functional groups in the surface of mesoporous silicas was studied by lanthanide ions sorption experiments. All of the CMPO modified OMMs favors the smaller Eu(III) and Nd(III) cations than La(III) for relative larger ionic radius.

Metallorganic Chemical Vapor Deposition and Characterization of TiO2 Nanoparticles

  • Jung, Oh-Jin;Kim, Sam-Hyeok;Cheong, Kyung-Hoon;Li, W.;Saha, S. Ismat
    • Bulletin of the Korean Chemical Society
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    • v.24 no.1
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    • pp.49-54
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    • 2003
  • TiO₂nanoparticles were synthesized using the metallorganic chemical vapor deposition process. Particles with and without metal ion dopants were obtained. X-ray photoelectron and energy dispersive X-ray spectroscopic measurements confirmed the stoichiometry of the TiO₂nanoparticles. X-ray diffraction patterns showed a polycrystalline anatase structure of TiO₂. Transmission electron microscopy revealed that these particles are of nanoscale dimensions. Exact particle size and size distribution analyses were carried out by dynamic light scattering. The average particle size was determined to be 22 nm. The nanosize particles provided large surface area for photocatalysis and a large number of free surface-charge carriers, which are crucial for the enhancement of photocatalytic activity. To improve the photocatalytic activity, metal ions, including transition metal ions $(Pd^{2+},\;Pt^{4+},\;Fe^{3+})$ and lanthanide ion $(Nd^{3+})$ were added to pure TiO₂nanoparticles. The effects of dopants on photocatalytic kinetics were investigated by the degradation of 2-chlorophenol under an ultraviolet light source. The results showed that the TiO₂nanoparticles with the metal ion dopants have higher photocatalytic activity than undoped TiO₂. The $Nd^{3+}$ ion of these dopant metal ions showed the highest catalytic activity. The difference in the photocatalytic activity with different dopants is related to the different ionic radii of the dopants.

Structure analysis, and magnetic study of a new Gd-metal-organic framework single crystal grown by the slow-evaporation method (증발법으로 합성된 신규 가돌리늄 금속-유기골격체의 단결정 구조 분석 및 자성학적 특성 연구)

  • Song, Jeong Hwa
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.32 no.5
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    • pp.199-204
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    • 2022
  • A new three-dimensional Gd-MOF, [Gd(p-XBP4)4(H2O)]·W(CN)8; (1; p-XBP4 = N,N'-p-phenylenedimethylenbis (pyridin-4-one)) has been synthesized by slow-evaporation and its crystal structure was characterized by single-crystal X-ray diffraction (SCXRD) analysis. For each GdIII ion, there are seven coordination sites, which are occupied by six oxygen atoms of six p-XBP4 ligands and one oxygen atom from the water molecule. The [W(CN)8]3- anion exists for charge balance with cationic framework. The GdII ions are interconnected by the p-XBP4 ligand to form the three-dimensional structure. Considering the magnetic property of lanthanide ions, magnetic studies of Gd-MOF were investigated by direct-current (DC) magnetic susceptibilities measurements.

Photocatalytic Decomposition of Methylene Blue over Sm Ion Doped Ti-SBA-15 Catalysts (Sm이온이 도핑된 Ti-SBA-15 촉매에서의 메틸렌블루의 광촉매 분해 반응)

  • Jung, Won-Young;Lee, Seong-Hun;Hong, Seong-Soo
    • Journal of Environmental Science International
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    • v.20 no.4
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    • pp.511-517
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    • 2011
  • Ti-SBA-15 catalysts doped with samarium ion were synthesized using conventional hydrothermal method. The physical properties of Sm/Ti-SBA-15 catalysts have been characterized by XRD, FT-IR, DRS and PL. In addition, we have also examined the activity of these materials on the photocatalytic decomposition of methylene blue. The Sm/ Ti-SBA-15 was shown to have the mesoporous structure regardless of Sm ion doping. With doping amount of 1% lanthanide ion, the pore size and pore volume of Sm(Er, Cs)/Ti-SBA-15 decreased and the surface area increased. For the purpose of vibration characteristics on the Ti-SBA-15 and Sm/Ti-SBA-15 photocatalysts, the IR absorption at 960 $cm^{-1}$ commonly accepted the characteristic vibration of Ti-O-Si bond. 1% of Sm/Ti-SBA-15 had the highest photocatalytic activity on the decomposition of methylene blue but the catalysts doped with Er ions had lower activity in comparison with pure Ti-SBA-15 catalyst.

Superconductivity of infinite layer cuprate

  • Lee, Sung-Ik;Jung, Chang-Wook;Kim, Ji-Yeon;Kim, Heon-Jung;Park, Min-Seok
    • 한국초전도학회:학술대회논문집
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    • v.10
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    • pp.1-1
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    • 2000
  • The infinite layer compound $ACuO_2$, (A-Alkaline earth) consists of infinite stacking of $CuO_2$ planes separated only by alkaline earth ions. This compound attracted much attention because it contains only key ingredient of all cuprate high temperature superconductor; $CuO_2$ plane with controllable carrier concentration without charge reservoir block. High pressure synthesis method has been found to be preferable for this system due to its ability of doping various lanthanide ion into A site with larger superconducting volume fraction. But rigorous study on this rudimentary compound has been hindered by insufficient quality of sample. Especially superconductlng volume fraction was often too small to identify its origin. In this presentation, we report high pressure synthesis of $Sr_{0.9}Ln_{0.1}CuO_2$ (Ln=La, Sm). By controlling the heating temperature precisely during high pressure synthesis we could have superconductors with quite high superconducting volume fraction for this compound. The magnetic properties of the graln aligned samples show very different behavior compared to the cuprate high temperature superconductors. Details will be discussed.

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Preparation and Luminescent Properties of a Novel Carbazole Functionalized Bis-β-diketone Ligand and Corresponding Eu(III) and Tb(III) Complexes

  • Zhang, Wei;Liu, Chang-Hui;Tang, Rui-Ren;Tang, Chang-Quan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.10
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    • pp.2213-2216
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    • 2009
  • A novel carbazole functionalized bis-$\beta$-diketone type organic ligand, 1,1′-(2,6-bispyridyl)bis-3-(9-ethylcarbazole- 3-yl)-1,3-propanedione ($H_2L$) and its corresponding lanthanide complexes $Eu_2(L)_3\;and\;Tb_2(L)_3$ were successfully prepared. The ligand and complexes were characterized in detail based on FT-IR spectra, $^1H$ NMR and elemental analysis. The observed UV-Vis absorption and photoluminescence properties of the complexes were investigated, it shows that the Eu(III) and Tb(III) ions can be sensitized efficiently by the ligand ($H_2L$) to some extent, in particular, the complex $Tb_2(L)_3$ exhibits a more excellent luminescence property than the Eu(III) complex. Meanwhile, the introduction of the carbazole moiety can enlarge the $\Pi$-conjugated system of the ligand and enhance the luminescent intensity of the complexes. The results show that the complexes would be used as excellent luminescent materials.

The Stability Constant of Transition and Lanthanide Metal Ions Complexes with 15 Membered Macrocyclic Azacrown Ligands (거대고리 아자크라운화합물과 전이금속 및 란탄족금속이온의 착물의 안정도)

  • Hong, Choon-Pyo;Choi, Yong-Gu;Choppin, G.R.
    • Journal of the Korean Chemical Society
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    • v.48 no.6
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    • pp.577-582
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    • 2004
  • The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

Wavelength Conversion Lanthanide(III)-cored Complex for Highly Efficient Dye-sensitized Solar Cells

  • Oh, Jung-Hwan;Song, Hae-Min;Eom, Yu-Kyung;Ryu, Jung-Ho;Ju, Myung-Jong;Kim, Hwan-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2743-2750
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    • 2011
  • Lanthanide(III)-cored complex as a wavelength conversion material has been successfully designed and synthesized for highly efficient dye-sensitized solar cells, for the first time, since light with a short wavelength has not been effectively used for generating electric power owing to the limited absorption of these DSSCs in the UV region. A black dye (BD) was chosen and used as a sensitizer, because BD has a relatively weak light absorption at shorter wavelengths. The overall conversion efficiency of the BD/WCM device was remarkably increased, even with the relatively small amount of WCM added to the device. The enhancement in $V_{oc}$ by WCM, like DCA, could be correlated with the suppression of electron recombination between the injected electrons and $I_3{^-}$ ions. Furthermore, the short-circuit current density was significantly increased by WCM with a strong UV light-harvesting effect. The energy transfer from the Eu(III)-cored complex to the $TiO_2$ film occurred via the dye, so the number of electrons injected into the $TiO_2$ surface increased, i.e., the short-circuit current density was increased. As a result, BD/WCM-sensitized solar cells exhibit superior device performance with the enhanced conversion efficiency by a factor of 1.22 under AM 1.5 sunlight: The photovoltaic performance of the BD/WCM-based DSSC exhibited remarkably high values, $J_{sc}$ of 17.72 mA/$cm^2$, $V_{oc}$ of 720 mV, and a conversion efficiency of 9.28% at 100 mW $cm^{-2}$, compared to a standard DSSC with $J_{sc}$ of 15.53 mA/$cm^2$, $V_{oc}$ of 689 mV, and a conversion efficiency of 7.58% at 100 mW $cm^{-2}$. Therefore, the Eu(III)-cored complex is a promising candidate as a new wavelength conversion coadsorbent for highly efficient dye-sensitized solar cells to improve UV light harvesting through energy transfer processes. The abstract should be a single paragraph which summaries the content of the article.

Macrocyclic Complexes of Actinide and Lanthanide Metals (Ⅰ). Formation and Properties of Cation Complexes with Macrocyclic Ligands (악틴 및 란탄족금속의 거대고리 착물 (제 1 보). 거대고리 리간드의 금속착물의 형성과 성질)

  • Jeong, O Jin;Choe, Chil Nam;Yun, Seok Jin;Son, Yeon Su
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.143-158
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    • 1990
  • Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

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The Co-luminescence Groups of Sm-La-pyridyl Carboxylic Acids and the Binding Characteristics between the Selected Doped Complex and Bovine Serum Albumin

  • Yang, Zhengfa;Tang, Ruiren;Tang, Chunhua
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1303-1309
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    • 2012
  • A novel ligand N,N'-(2,6-pyridinedicarbonyl)bis[N-(carboxymethyl)] (L1) was designed and synthesized. Four co-luminescence groups of Sm-La-pyridyl carboxylic acids systems were researched, which are $K_4Sm_{(1-x)}-La_x(L_1)Cl_3{\cdot}y_1H_2O$, $K_4Sm_{(1-x)}La_x(L_2)Cl_3{\cdot}y_2H_2O$, $K_6Sm_{2(1-x)}La_{2x}(L_3)Cl_6{\cdot}y_3H_2O$, $K_4Sm_{(1-x)}La_x(L_4)Cl_3{\cdot}y_4H_2O$. The results indicated the addition of La(III) could sensitize the luminescence of Sm(III) obviously in a certain range, enhancing emission intensity of Sm-pyridyl carboxylic acids relative to the undoped ones. The optimal mole percentages of La(III) in the mixed ions for $L_1$, $L_2$, $L_3$, $L_4$ were confirmed to be 0.6, 0.5, 0.3, 0.6, respectively. The mechanism of the fluorescence enhancement effect was discussed in detail. Furthermore, the binding interaction of $K_4Sm_{0.4}La_{0.6}(L_4)Cl_3{\cdot}5H_2O$ with bovine serum albumin (BSA) have been investigated due to its potential biological activity. The binding site number n was equal to 1.0 and binding constant $K_a$ was about $2.5{\times}10^5\;L{\cdot}mol^{-1}$.