• Journal of the Korean Electrochemical Society
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• v.15 no.4
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• pp.256-263
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• 2012

This study was performed to investigate the separation of cesium cations by using an electrochemical ion exchanger of nickel hexacyanoferrate($KNiFe(CN)_6$) film electrode. Potential, current, and charge passing through the cyclic voltammograms were measured in singular and binary solutions of 1.0M $NaNO_3$ and 1.0M $CsNO_3$. Before and after each experiment, the structural morphology and atomic composition of $KNiFe(CN)_6$ were analyzed by SEM and EDS, respectively. The ion selectivity of $KNiFe(CN)_6$ was also observed by the voltammograms and atomic compositions measured in the solution alternated between sodium and cesium. As the result of this study, it was found that the electrically switched $KNiFe(CN)_6$ ion exchanger had the significant advantage of 40 times or longer durability than conventional organic or inorganic ion exchanger. It was also shown that the $KNiFe(CN)_6$ ion exchanger had high selectivity for cesium over sodium.

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.384-392
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• 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 the Korean Electrochemical Society
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• v.23 no.1
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• pp.11-17
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• 2020

The Prussian blue analogues of Fe₂(CN)₆ and Na_xFe₂(CN)₆ are prepared by precipitation method and evaluated the electrochemical characteristics as positive electrode materials for lithium-ion batteries (LIBs) because of their low cost. Fe₂(CN)₆ shows a low reversible capacity of 34.6 mAh g^-1, whereas sodium-containing Na_xFe₂(CN)₆ exhibits a reversible capacity of 107.5 mAh g^-1 when the discharge process proceeds first. When charging is first carried out to remove sodium in the structure, the reversible capacity of 114.1 mAh g^-1 is achieved and the cycle performance is further improved. In addition, Na_x-Fe₂(CN)₆ is synthesized at 0℃, room temperature (RT), and 60℃, respectively. Regardless of the synthesis temperature, Na_xFe₂(CN)₆ shows similar initial reversible capacity, but the crystallite size is formed smaller and improved cycle performance when synthetic temperature is lower. The sample synthesized at 0℃ shows a reversible capacity of 86.4 mAh g^-1 at the 120^th cycle and maintains 76.8% of the initial capacity.

• Korean Journal of Materials Research
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• v.23 no.12
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• pp.672-679
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• 2013

$Fe_4[Fe(CN)_6]_3$ coated on a mica or $TiO_2$/mica surface as infrared reflective blue pigment was prepared by a hydrothermal method. $Fe_4[Fe(CN)_6]_3$, used as coloring agent, was uniformly coated on mica or $TiO_2$/mica under the optimized condition of a 1.2 : 1 weight ratio between iron(III) chloride hexahydrate and potassium ferrocyanidetrihydrate at the initial pH level of 4.5 at $70^{\circ}C$. The infrared (IR)-reflective pigments were characterized by SEM, Zeta-potenial, FT-IR, and UV-VIS NIR spectrophotometry. Especially the CIE color coordinate and total solar reflectance(TSR) properties of the pigments were investigated in relation to variation of the coating and coated substrate thicknesses. Isolation-heat paint was prepared with 20 wt% blue pigments fully dispersed in acryl-urethane resin and several additives to coat the film uniformly. The films were also measured with CIE color coordinate, TSR, and the surface temperature was recorded by an isolation-heat measuring system. The pigments and films of $Fe_4[Fe(CN)_6]_3$ coated on mica and $TiO_2$/mica showed high TSR values compared with the TSR value of $Fe_4[Fe(CN)_6]_3$ itself. According to the increase of TSR value, the property of isolation-heat is effective. To realize the optimal blue color, we applied the the pigment to $TiO_2$ coated mica(TM(b)) which has blueish interference color. The pigment of $Fe_4[Fe(CN)_6]_3$ coated on TM(b) shows a strong blue color compared with that of $Fe_4[Fe(CN)_6]_3$ coated on $TiO_2$/Mmca(TM(w)), which has a whitish interference color.

• Bulletin of the Korean Chemical Society
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• v.7 no.1
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• pp.36-38
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• 1986

The Ferricyanide-sensing electrodes were prepared with $Ag_2S\;and\;Ag_3Fe(CN)_6$ (mole ratio 3:1-7:1). The 5:1 $(Ag_2S:Ag_3Fe(CN)_6)$ composition is superior to others in terms of potentiometric response, rapidity of response and reproducibility. Testing was done over the concentration range $10^{-1}M{\sim}10^{-6}M\; Fe(CN)_6^{3-}$ at pH 6.8 with constant ionic strength. The concentration-potential curve was linear and coincided with the Nernstian slope (19.7 mV/decade). Interfering ions were $I^-,\;Br^-,\; SCN^-\;and\;Fe(CN)_6^{4-}$ and the life time of this electrode was 3 weeks. This electrode could be used as the indicator electrode for measuring the ferricyanide and ferrocyanide.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.6 no.4
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• pp.571-583
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• 1996

The electrochemical behavior on electrographite and graphite foil electrode with porous surface in 0.5 M $K_{2}SO_{4}$ solution with 1 mM $[Fe(CN)_{6}]^{3-}/[Fe(CN)_{6}]^{4-}$ have been characterized by impedance spectroscopy. In cyclic voltammograms, relative high current according to structure of porous surface for graphite materials was represented, and indicated hgih double layer capacitance on graphite foil. The faraday-impedance and the change of impedance spectrum on both graphite materials were not remarkable during polarization by reaction of field transport. Chemical adsorption was represented on electrographite and was depended highly at anodic polarization.

• Journal of the Korean Chemical Society
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• v.68 no.2
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• pp.82-86
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• 2024

This paper presents the solid-state synthesis of insoluble Prussian blue (Fe₄[Fe(CN)₆]₃·xH₂O, PB) in a ball mill, utilizing the fundamental components of PB. Solid-state synthesis offers several advantages, such as being solvent-free, quantitative, and easily scalable for industrial production. Traditionally, the solid-state synthesis of PB has been limited to the reaction between iron(II/III) ions and hexacyanoferrate(II/III) complex ions, essentially an extension of the solution-based coprecipitation method to solid-state reaction. Taking a bottom-up approach, a reaction is designed where the reactants consist of the basic building blocks of PB: Fe²⁺ ions and CN^- ions. The reaction, with a molar ratio of Fe²⁺ and CN^- corresponding to 1:2.8, yields PB, while a ratio of 1:6.6 results in a mixture of potassium hexacyanoferrate(II) (K₄Fe(CN)₆), potassium chloride (KCl), and potassium cyanide (KCN). This synthetic approach holds promise for environmentally friendly methods to synthesize multimetallic PB with maximum entropy in nearly quantitative yield.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• Journal of the Korean Magnetics Society
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• v.22 no.4
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• pp.125-129
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• 2012

By employing soft x-ray absorption spectroscopy (XAS) and soft x-ray magnetic circular dichroism (XMCD), the electronic structures of molecule-based nano bioparticles, such as Helicobacter pylori ferritin (H. pylori ferritin), Heme, $NaM[Fe(CN)_6]{\cdot}H_2O$-type Prussian Blue (M=Co, Ni) analogue, have been investigated. The measured Fe 2p XAS spectra reveal that Fe ions are trivalent ($Fe^{3+}$) in H. pylori ferritins, while they are in the $Fe^{2+}-Fe^{3+}$ mixed-valent states in $NaM[Fe(CN)_6]{\cdot}H_2O$ Prussian Blue analogues (M=Co, Ni). According to the Fe 2p XMCD spectrum of high-state H. pylori ferritin, all the $Fe^{3+}$ ions have the same local symmetry and their magnetic moments are aligned in the same direction. It is also found that the Fe 3d orbitals in $NaM[Fe(CN)_6]{\cdot}H_2O$ have a strong covalent bonding to $(CN)^-$ ligands, but with a very weak bonding to the 2p orbitals of O ligands.

• Journal of Korean Society on Water Environment
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• v.25 no.6
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• pp.979-983
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• 2009

The mean pH of wastewater discharged from the plating process is 2, so a less amount of alkali is required to raise pH 2 to 5. In addition, if sodium sulfite is used to raise pH 5 to 9 in the secondary treatment, caustic soda or slaked lime is not necessary or only a small amount is necessary because sodium sulfite is alkali. Thus, it is considered desirable to use only $FeSO_4{\cdot}7H_2O$ in the primary treatment. At that time, the free cyanide removal rate was highest as around 99.3%, and among heavy metals, Ni showed the highest removal rate as around 92%, but zinc and chrome showed a low removal rate. In addition, the optimal amount of $FeSO_4{\cdot}7H_2O$ was 0.3g/L, at which the cyanide removal rate was highest. Besides, the free cyanide removal rate was highest when pH value was 5. Of cyanide removed in the primary treatment, the largest part was removed through the precipitation of ferric ferrocyanide: $[Fe_4(Fe(CN)_6]_3$, and the rest was precipitated and removed through the production of $Cu_2[Fe(CN)_6]$, $Ni_2[Fe(CN)_6]$, CuCN, etc. Furthermore, it appeared more effective in removing residual cyanide in wastewater to mix $Na_2SO_3$ and $Na_2S_2O_5$ at an optimal ratio and put the mixture than to put them separately, and the optimal weight ratio of $Na_2SO_3$ to $Na_2S_2O_5$ was 1:2, at which the oxidative decomposition of residual cyanide was the most active. However, further research is required on the simultaneous removal of heavy metals such as chrome and zinc.