• Composites Research
• /
• v.32 no.6
• /
• pp.355-359
• /
• 2019

The high efficient water splitting system should involve the reduction of high overpotential value, which was enhanced by the electrocatalytic reaction efficiency of catalysts, during the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) reaction, respectively. Among them, transition metal-based compounds (oxides, sulfides, phosphides, and nitrides) are attracting attention as catalyst materials to replace noble metals that are currently commercially available. Herein, we synthesized optimal monodisperse Co₃[Co(CN)₆]₂ PBAs by FESEM, and confirmed crystallinity by XRD and FT-IR, and thermal behavior of PBAs via TG-DTA. Also, we synthesized monodispersed Co₃O₄ nanocubes by calcination of Co₃[Co(CN)₆]₂ PBAs, confirmed the crystallinity by XRD, and proceeded OER measurement. Finally, the synthesized Co₃O₄ nanocubes showed a low overpotential of 312 mV at a current density of 10 mA·cm^-2 with a low Tafel plot (96.6 mV·dec^-1).

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.27 no.3
• /
• pp.110-114
• /
• 2017

$NiO/NiCo_2O_4$ nanocubes were successfully synthesized via the calcination process of $Ni_3[Co(CN)_6]_2$ PBAs. The prepared monodispersed $Ni_3[Co(CN)_6]_2$ PBAs were aggregated by 'self-assembly' of the nuclei generated during the synthesis reaction. The self-assembly rate of the particles is affected by the temperature and the amount of surfactant SDBS (sodium dodecylbenzenesulfonate). FESEM analysis shows that monodispersed 200 nm PBA nanocubes are obtained at 0.25 g SDBS and $60^{\circ}C$ temperature. Thermal behavior was confirmed by thermogravimetric-differential thermal analysis (TG-DTA) to determine optimal calcination conditions. Then, field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) analyzes were performed to investigate the morphology and crystallinity of the particles precursors and $NiO/NiCo_2O_4$ nanocubes.

• Journal of the Korean Chemical Society
• /
• v.28 no.6
• /
• pp.384-392
• /
• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Journal of Sensor Science and Technology
• /
• v.29 no.4
• /
• pp.215-219
• /
• 2020

MnCo₂S₄/CoS₂ electrode with highly accessible electroactive sites is prepared using the hydrothermal method. The electrode exhibits an areal capacitance of 0.75 Fcm^-2 at 6 mAcm^-2 in 1 M KOH. The capacitance is further increased to 2.06 Fcm^-2 by adding K₃Fe(CN)₆ and K₄Fe(CN)₆ (a redox couple) to KOH. This increment is associated with the redox-active properties of cobalt and manganese transition metals, as well as the ion pair of [Fe(CN)₆]^-3/[Fe(CN)₆]^-4. The capacitance retention of the MnCo₂S₄/CoS₂ electrode is 87.5% for successive 4000 charge-discharge cycles at 10 mAcm^-2 in a composite electrolyte system of KOH and ferri/ferrocyanide. The capacitance enhancement is supported by the lowest equivalent series resistance (0.62 Ωcm^-2) of MnCo₂S₄/CoS₂ in the presence of redox additive couple compared with the bare KOH electrolyte.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.11
• /
• pp.961-966
• /
• 1994

Oligomerization of phenylacetylene is catalyzed by $Rh(ClO_4)(CO)(PPh_3)_2$ (Rh-1), $[Rh(CO)(PPh_3)_3]ClO_4$ (Rh-2), $[Rh(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, Rh-3; $(PPh_3)(PhCN)$, Rh-4; $(PhCN)_2$, Rh-5), $[Rh(C_3H_5)(Cl)(CO)(SbPh_3)_2]ClO_4$ (Rh-6), $[Ir(COD)L_2]ClO_4 (L_2=(PPh_3)_2$, $Ir-1; (PPh_3)(PhCN)$, $Ir-2; (PhCN)_2$, Ir-3; (AsPh_3)(PhCN)$, $Ir-4; Ph_2PCH_2CH_2PPh_2$, Ir-5; COD, Ir-6 and 2,2'-dipyridyl, Ir-7), $Ir(ClO_4)(CO)(PPh_3)_2$, $Ir-8, [Ir(PhCN)(CO)(PPh_3)_2]ClO_4$, Ir-9 to produce dimerization products, 1,3-diphenylbut-1-yn-3-ene, 1, (E)-1,4-diphenylbut-1-yn-3-ene, 2 and (Z)-1,4-diphenylbut-1-yn-3-ene, 3, and cyclotrimerization products, 1,3,5-triphenylbenzene, 4 and 1,2,4-triphenylbenzene, 5. Product distribution of the oligomers varies depending on various factors such as the nature of catalysts, reaction temperature, counter anions and excess ligand present in the reaction mixtures. Increasing reaction temperature in general increases the yield of the cyclotrimerization products. Exclusive production of dimer 1 and trimer 4 can be obtained with Ir-1 at 0 $^{\circ}$C and with Ir-2 in the presence of excess PhCN (or $CH_3CN$) at 50 $^{\circ}$C, respectively. Dimer 2 (up to 81%) and trimer 5 (up to 98%) are selectively produced with Rh-1 at 50 and 100 $^{\circ}$C respectively. Production of 3 is selectively increased up to 85% by using $PF_6$- salt of $[Ir(COD)(PPh_3)_2]$+ at 25 $^{\circ}$C. Addition of $CH_3I$ to Rh-1 produces $CH_3PPh_3^+I-$ and increases the rate of oligomerization(disappearance of phenylacetylene). Among the metal compounds investigated in this study, Ir-1 catalyzes most rapidly the oligomerization where the catalytically active species seems to contain lr(PPh3)2 moiety. The stoichiometric reaction of phenylacetylene wth Ir-9 at 25 $^{\circ}$C quantitatively produces hydridophenyl-ethynyl iridium(III) complex, $[lr(H)(C{\equiv}CPh)(PhCN)(CO)(PPh_3)_2]ClO_4$ (Ir-11), which seems to be an intermediate for the oligomerization.

• Bulletin of the Korean Chemical Society
• /
• v.8 no.3
• /
• pp.179-183
• /
• 1987

Reactions of $Rh(ClO_4)(CO)(AsPh_3)_2$ with unsaturated nitriles and aldehyde, L, produce a series of new cationic rhodium (I) complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ (L = $CH_2$ = CHCN, $CH_2$ = C($CH_3$)CN, trans-$CH_3CH$ = CHCN, $CH_2$ = CH$CH_2$CN, trans-$C_6H_5CH$ = CHCN, and trans-$C_6H_5CH$ = CHCHD) where L are coordinated through the nitrogen and oxygen, respectively but not through the ${\pi}$-system of the olefinic group. Dissociation constants for the reaction, $[RhL(CO)(AsPh_3)_2]ClO_4$ $\rightleftharpoons$ $Rh(ClO_4)(CO)(AsPh_3)_2$ + L, have been measured to be $1.20{\times}10^{-4}$ M (L = $CH_2$ = CHCN), $1.05{\times}10^{-4}$ M (L = $CH_2$ = C($CH_3$)CN, $3.26{\times}10^{-5}$ M (L = trans-$CH_3$CH = CHCN) and $6.45{\times}10^{-5}$ M (L = $CH_2$ = CH$CH_2$CN) in chlorobenzene at $25^{\circ}C, and higher than those of triphenylphosphine complexes, $[RhL(CO)(AsPh_3)_2]ClO_4$ where L are the corresponding nitriles that are coordinated through the nitrogen atom. The differences in dissociation constants seem to be predominantly due to the differences in ${\Delta}H$ (not due to the differences in ${\Delta}S$). The weaker Rh-N (unsaturated nitriles) bonding in $AsPh_3$ complexes than in $PPh_3$ complexes (based on ${\Delta}H$ values) suggests that the unsaturated nitriles in 2∼5 are good ${\sigma}$-donor and poor ${\pi}$-acceptor.

• Journal of the Korean Chemical Society
• /
• v.47 no.6
• /
• pp.547-552
• /
• 2003

Separation and determinations of Co(II) and Ni(II) ions as their 4-(2-pyridylazo)resorcinol(PAR) chelates by reversed-phase capillary high-performance liquid chromatography(RP-CpHPLC) were performed. Among many capillary columns, Vydac C4 column was selected and acetonitrile solution was used as mobile phase. The effect of pH and MeCN concentration(%) on the retention factor, k and peak intensity was examined and discussed. As a results, it was found that 22.5% MeCN and pH 5.60 was adequate as mobile phase for the separation of the two metal ions and determination of Co(II) ion, but the mobile phase condition for Ni(II) ion determination was 22.5% MeCN of pH 7.20. Detection limit(D.L., S/N=3) of Co(II) and Ni(II) ions were $2.0{\times}10{-7}$ M(14.9 ppb) and $1.0{\times}10{-6}$ M(59.2 ppb), respectively.

• Journal of the Korean Chemical Society
• /
• v.33 no.3
• /
• pp.273-280
• /
• 1989

The spectra of the $Co^{II}CyDTA$(CyDTA: cyclohexyldiaminetetraacetic acid) complex have been measured in aqueous solution of pH = 6-13.2. The red shift of the spectrum in the more basic solution was ascribed to the transformation of $CoCyDTA^{2-}$ into $CoCyDTA(OH)^{3-}$. The equilibrium constant, $K_{OH} = [CoCyDTA(OH)^{3-}]/[CoCyDTA^{2-}][OH^-]$ was $75M^{-1}$ at $40^{\circ}C$. The electron transfer reactions of $CoCyDTA^{2-}$ and $CoCyDTA(OH)^{3-}$ with $Fe(CN)_6^{3-}$ have been studied using spectrophotometric technique in the range of pH applied to the determination of equilibrium constant. The pseudo first-order rate constants observed ($k_{obs}$) were not changed upto pH = 10.8, but increased with increasing pH in the range of pH = $10.8{\sim}13.0$. The rate law reduced in the range of pH = 6-13 was $k_{obs} = (k_3[CoCyDTA^{2-}] + k_4[CoCyDTA(OH)^{3-}])/(1+K_1[CoCyDTA^{2-}])$. The rate constants of the reactions (3a) and (3b), $k_3$ and $k_4$ respectively have been determined to be 0.529 and $4.500M^{-1}sec^{-1}$ at $40^{\circ}C$. The activation entropies (147{\pm}1.1JK^{-1} mol^{-1}$ at pH = 10.8) and activation volumes $(6.25cm^3mol^{-1}, pH = 10.8)$ increased with increasing pH, while the activation enthalpy (12.44 ${\pm}$ 0.20 kcal/mole) was independent of pH. Using the pH effect on the rate constants, the activation entropies and the activation volumes, the mechanism of the electron transfer reaction for $Co^{II}-Fe^{III}$ system was discussed.

• Journal of the Korean Chemical Society
• /
• v.9 no.2
• /
• pp.101-105
• /
• 1965

Spectrophotometric method for the determination of Co(Ⅱ) is developed based on the fact that Co(Ⅱ) forms a stable red complex with 7-nitroso-8-hydroxyquinoline-5-sulfonate at pH 4. 5. The absorbance is measured at 528$m{\mu}$, $25^{\circ}C$. Beer's law is followed in the concentration range of 0. 3 to 6. 0 p.p.m. of Co(Ⅱ) and molar extinction coefficient of the complex was $1.1{\times}10^4$. Of the diverse ions checked, Fe(Ⅱ), Fe(Ⅲ), Cu(Ⅱ), Mn(Ⅱ), Hg(Ⅰ), CN-, EDTA interfere. The composition of the complex is found to be 3:1 ligand to metal species by mole ratio and continuous variation methods.

• Journal of Energy Engineering
• /
• v.5 no.1
• /
• pp.56-64
• /
• 1996

The objective of this investigation is to establish the rejection characteristics of caesium and cobalt from radioactive liquid waste by chemical/ultrafiltration process. An extensive experimental investigation was conducted with inactive caesium and cobalt ions, utilizing ultrafiltration stirred cell. Caesium and cobalt could be effectively removed from waste solution using copper ferrocyanide and polyarcylic acid(PAA). The rejection dependence of the caesium was found to be a function of caesiun to potassium copper ferrocyanide feed molar ratio. The binding behavior of caesium on K$_2$Cu$_3$(Fe(CN)$\sub$6/)$_2$, particles was explained in terms of a Langmuir adsorption isotherm. When Cs/K$_2$Cu$_3$(Fe(CN)$\sub$6/)$_2$molar ratio was 1.5, the removal of caesium was the most efficient. The rejection efficiency of cobalt is dependent upon various parameters such as pH, cobalt concentration and PAA concentration. The rejection behavior of cobalt was explained in term of a equilibrium model taking into account the reaction between the ligand group, the proton and the cobalt ion. At the conditions of PAA/Co ratio of 2 and pH of 5.6, the removal of cobalt was over 90%. Also, the effect of chemical addition sequence for the simultaneously removal of caesiun and cobalt was discussed.