• Korean Journal of Materials Research
• /
• v.26 no.5
• /
• pp.250-257
• /
• 2016

Octahedral $Co_3O_4$/carbon nanofiber (CNF) composites are fabricated using electrospinning and hydrothermal methods. Their morphological characteristics, chemical bonding states, and electrochemical properties are used to demonstrate the improved photovoltaic properties of the samples. Octahedral $Co_3O_4$ grown on CNFs is based on metallic Co nanoparticles acting as seeds in the CNFs, which seeds are directly related to the high performance of DSSCs. The octahedral $Co_3O_4$/CNFs composites exhibit high photocurrent density ($12.73mA/m^2$), superb fill factor (62.1 %), and excellent power conversion efficiency (5.61 %) compared to those characteristics of commercial $Co_3O_4$, conventional CNFs, and metallic Co-seed/CNFs. These results can be described as stemmnig from the synergistic effect of the porous and graphitized matrix formed by catalytic graphitization using the metal cobalt catalyst on CNFs, which leads to an increase in the catalytic activity for the reduction of triiodide ions. Therefore, octahedral $Co_3O_4$/CNFs composites can be used as a counter electrode for Pt-free dye-sensitized solar cells.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.7 no.2
• /
• pp.244-252
• /
• 1997

The pseudo-spinel type solid solution, $LiAl_{2.5}/Fe_{2.5}O_8$ was prepared by reaction of $LiCO_3, Al_2O_3, Fe_2O_3$ mixture at 1620K, which can be used for cathode material in lithium batteries. Its structure was investigated by Rietveld profile-analysis of XRD in detail. The space group of solid solution is $P4_3$32(a=8.1293$\AA$) and the final residual index of structure refinement was about 5%. Cations $Al^{3+}, Fe^{3+}$ are located at both tetra- and octahedral-coordination and $Li^+$ ions are occupied in the octahedral 4b-, 12d-site of the inverse spinel.

• Journal of the Korean Magnetics Society
• /
• v.16 no.1
• /
• pp.23-27
• /
• 2006

By substituting Mn or Cr for Co in inverse spinel $CoFe_2O_4,\;Mn_xCo_{1-x}Fe_2O_4\;and\;Cr_xCo_{1-x}Fe_2O_4$ and thin films were prepared by sol-gel method and their structural and magnetic properties were investigated. X-ray diffraction indicates that the cubic lattice constant increase for the Mn substitution while it hardly changes for the Cr substitution. Substitution of $Mn^{2+}$ for octahedral $Co^{2+}$ sites can explain the increase of lattice constant in $Mn_xCo_{1-x}Fe_2O_4$. On the other hand, Substitution of $Cr^{3+}$ for octahedral $Co^{2+}$ and subsequent reduction of $Fe^{3+}$ ion into $Fe^{2+}$ are expected to happen. Mossbauer spectroscopy measurements on $Cr_xCo_{1-x}Fe_2P_4$ indicate the existence of tetrahedral $Fe^{2+}$ ions that are created through reduction of tetrahedral $Fe^{3+}$ ions in order to compensate charge imbalance happened by $Cr^{3+}$ substitution for octahedral $Co^{2+}$ sites. On the other hand, no $Fe^{2+}$ ions were detected by Mossbauer spectroscopy for $Mn_xCo_{1-x}Fe_2O_4$. A migration of $Fe^{3+}$ ions from octahedral to tetrahedral sites In $Mn_xCo_{1-x}Fe_2O_4$ was detected by Mossbauer spectroscopy for x>0.47. Vibrating sample magnetometry measurements on the samples at room temperature revealed that the saturation magnetization increases by Mn and Cr substitution for certain range of x, qualitatively explainable in terms of the comparison of spin magnetic moment among the related transition-metal ions.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.10
• /
• pp.1050-1052
• /
• 1997

The complexes M(CO)4-1,2-(PPh2)2-1,2-C2B10H10 (M=Cr 2a, Mo 2b, W 2c) have been prepared in good yields from readily available bis-diphenylphosphino-o-carboranyl ligand, closo-1,2-(PPh2)2-1,2-C2B10H10 (1), by direct reaction with Group Ⅵ metal carbonyls. The infrared spectra of the complexes indicate that there is an octahedral disposition of chelate bis-diphenylphosphino-o-carboranyl ligand around the metal atom. The crystal structure of 2a was determined by X-ray diffraction. Complex 2a crystallizes in the monoclinic space group P21/n with cell parameters a = 12.2360(7), b = 17.156(1), c = 16.2040(6) Å, V = 3354.1(3) Å3, and Z =4. Of the reflections measured a total of 2514 unique reflections with F2 > 3σ(F2) was used during subsequent structure refinement. Refinement converged to R1 = 0.066 and R2 = 0.071. Structural studies showed that the chromium atom had a slightly distorted pseudo-octahedral configuration about the metal center with two phosphine groups of o-carborane occupying the equatorial plane cis-orientation to each other. These metal carbonyl complexes are rapidly converted to the corresponding metal carbene complexes, [(CO)3M=C(OCH3)(CH3)]-1,2-(PPh2)2-1,2-C2B10H10 (M= Cr 3a, Mo 3b, W 3c), via alkylation with methyllithium followed by O-methylation with CF3SO3CH3.

• Journal of the Korean Magnetics Society
• /
• v.15 no.2
• /
• pp.109-112
• /
• 2005

Electronic and magnetic properties of $Ti_{1-x}M_xO_{2-\delta}$ (M=Co and Fe) thin films grown by sol-gel method have been investigated. Anatase and rutile $Ti_{1-x}Co_xO_{2-\delta}$ films were successfully grown on $Al_2O_3$ (0001) substrates and exhibited p-type electrical conductivity while the undoped films n-type conductivity. Room temperature vibrating sample magnetometry measurements on the anatase and rutile $Ti_{1-x}Co_xO_{2-\delta}$ films with same x ($=4.8 at.{\%}$) showed quite similar magnetic hysteresis curves with the saturation magnetic moment of $\~4 {\mu}_B$ per Co ion despite their differences in structural and electronic properties. Such giant magnetic moment is attributable to the unquenched orbital moment of the $Co^{2+}$ ions substituting the octahedral $Ti^{4+}$ sites. Similar ferromagnetic behavior was observed for $Ti_{1-x}Fe_xO_{2-\delta}$ films that are highly resistive compared to the Co doped samples. Saturation magnetic moment was found to decrease for higher x, i.e., $\~2$ and $\~1.5 {\mu}_B$ per Fe ion for x=2.4 and 5.8 at. $\%$, respectively. Conversion electron $M\ddot{o}ssbauer$ spectroscopy measurements predicted the coexistence of $Fe^{2+}$ and $Fe^{3+}$ ions at the octahedral sites of $Ti_{1-x}Fe_xO_{2-\delta}$.

• Journal of the Korean Chemical Society
• /
• v.23 no.4
• /
• pp.198-205
• /
• 1979

A valence bond method of calculation of the dipole moments for octahedral $(M(III)0_3S_3)$ type complexes are developed, using $d^2sp^3 $hybrid orbitals of the central metal ions and the single basis set orbital of ligands. (M (III) =V (III), Cr (III), Mn (III), Fe (III), Co (III), Ru (III), Rh (III) and OS (III)). In this method the mixing coefficient of the valence basis sets for the central metal ion with the appropriate ligand orbitals is not required to be the same, differently from the molecular orbital method. The valence bond method is much more easier to calculate the dipole moments for octahedral complexes than the approximate molecular orbital method and the calculated results are also in the range of the experimental vaues.

• Journal of Magnetics
• /
• v.15 no.4
• /
• pp.159-164
• /
• 2010

The Zn, Co and Ni substituted manganese ferrite powders, $Mn_{1-x}$(Zn, Co, Ni)$_xFe_2O_4$, were fabricated by the solgel method, and their crystallographic and magnetic properties were studied. The Zn substituted manganese ferrite, $Zn_{0.2}Mn_{0.8}Fe_2O_4$, had a single spinel structure above $400^{\circ}C$, and the size of the particles of the ferrite powder increased when the annealing temperature was increased. Above $500^{\circ}C$, all the $Mn_{1-x}$(Zn, Co, Ni)$_xFe_2O_4$ ferrite had a single spinel structure and the lattice constants decreased with an increasing substitution of Zn, Co, and Ni in $Mn_{1-x}$(Zn, Co, Ni)$_xFe_2O_4$. The Mossbauer spectra of $Mn_{1-x}Zn_xFe_2O_4$ (0.0$\leq$x$\leq$0.4) could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. For x = 0.6 and 0.8 they showed two Zeeman sextets and a single quadrupole doublet, which indicated they were ferrimagnetic and paramagnetic. And for x = 1.0 spectrum showed a doublet due to a paramagnetic phase. For the Co and Ni substituted manganese ferrite powders, all the Mossbauer spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. The variation of the Mossbauer parameters are also discussed with substituted Zn, Co and Ni ions. The increment of the saturation magnetization up to x = 0.6 in $Mn_{1-x}Co_xFe_2O_4$ could be qualitatively explained using the site distribution and the spin magnetic moment of substituted ions. The saturation magnetization and coercivity of the $Mn_{1-x}$(Zn, Co, Ni)$_xFe_2O_4$ (x = 0.4) ferrite powders were also compared with pure $MnFe_2O_4$.

• Journal of the Korean Magnetics Society
• /
• v.16 no.1
• /
• pp.1-5
• /
• 2006

The crystallographic properties and cation distribution of oxyspinels ferrite $Co_xFe_{1-x}O_4$ thin films have been explored by X-ray diffraction, vibrating sample magnetometer (VSM), and conversion electron $M\"{o}ssbauer$ spectroscopy (CEMS). Thin films are prepared by sol-gel method. Normal spinel structure is transformed to inverse spinel structure with increasing Co concentration CEMS results indicate that most of $Fe^{3+}$ ions are substituted to $Co^{3+}$ions. Accordingly $Co^{2+}$ ions on octahedral site migrate to tetrahedral site. Magnetic moment is decreased with increasing Co concentration, which means high spin $Fe^{3+}$ ions are replaced by low spin $Co^{3+}$.

• Journal of Korean Ophthalmic Optics Society
• /
• v.3 no.1
• /
• pp.223-228
• /
• 1998

Glass films of $SiO_2-TiO_2-M_xO_y$ (M = Co, Cr or Cu) have been prepared on soda-lime-silica slide glasses by the chemical solution method using a spin-coating technique. Commercially available tetraethyl orthosilicate, titanium trichloride, and cobalt-, chromium- and copper-nitrates were used as starting materials. No crystalline segregations of $Co_3O_4$, $Cr_2O_3$ and CuO were observed by X-ray diffraction ${\theta}-2{\theta}$ scans. From the optical transmission analysis, cobalt existed as $ Co^{2+}$ in tetrahedral coordination, chromium as $Cr^{6+}$ in tetrahedral symmetry and copper as $Cu^{2+}$ in octahedral coordination. Films with a crack-free and no texture exhibited homogeneous interfaces between the films and the substrates along the cross-section.

• Journal of the Korean Ceramic Society
• /
• v.28 no.11
• /
• pp.897-907
• /
• 1991

This study was conducted to research the formation and the color development of CoO-ZnO-Fe2O3-TiO2-SnO2 system for the purpose of synthesizing the spinel pigments which are stable at high temperature. After preparing CoO-ZnO-Fe2O3, in which CoO causes the color, as a basic composition, $\chi$CoO.(1-$\chi$)ZnO.Fe2O3 system, $\chi$CoO.(1-$\chi$)ZnO.TiO2 system and $\chi$CoO.(1-$\chi$)ZnO.SnO2 system were prepared with $\chi$=0, 0.2, 0.5, 0.7, 1.0 mole ratio respectively. The manufacturing was carried out at 128$0^{\circ}C$ for 90 minutes. These specimens were analyzed by the reflectance measurement and the X-ray diffraction analysis and the results were summarized as follows: 1. All of the specimens formed the spinel structure and were colored with stable yellow or blue. 2. As the content of CoO and Fe2O3 in the specimens being increased, the reflectance of each specimen was measured becoming lower and the colors were changed from yellow to greyish blue and from blue to dark blue. 3. As the substituting amount of Co2+ ion for Zn2+ ion in $\chi$CoO-ZnO-TiO2-SnO2 system being increased, the colors were changed from blue to greyish blue. The colors were changed from yellow to grayish green owing to the tetrahedral Co2+ ions being increased, the octahedral Co2+ ions being decreased with increasing the amount of Sn4+ ions. 4. CoO-ZnO-Fe2O3-TiO2-SnO2 system, in which Zn2+ was substituted with Co2+ and Fe3+ was substituted with Ti4+ and Sn4+, easily formed the spinel structure without regard to the amount of substitution or the ion owing to the selectivity of the coordination number: 4 of Zn2+, 4 of Co2+, 6 of Fe3+ or 6 of Ti4+ and Sn4+.