• Korean Journal of Materials Research
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• v.23 no.4
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• pp.219-226
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• 2013

Activated magnetite ($Fe_3O_{4-{\delta}}$) has the capability of decomposing $CO_2$ proportional to the ${\delta}$-value at comparatively low temperature of $300^{\circ}C$. To enhance the $CO_2$ decomposition capability of $Fe_3O_{4-{\delta}}$, $(Fe_{1-x}Co_x)_3O_{4-{\delta}}$ and $(Fe_{1-x}Mn_x)_3O_{4-{\delta}}$ were synthesized and then reacted with $CO_2$. $Fe_{1-x}Co_xC_2O_4{\cdot}2H_2O$ powders having Fe to Co mixing ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 were synthesized by co-precipitation of $FeSO_4{\cdot}7H_2O$ and $CoSO_4{\cdot}7H_2O$ solutions with a $(NH_4)_2C_2O_4{\cdot}H_2O$ solution. The same method was used to synthesize $Fe_{1-x}Mn_xC_2O_4{\cdot}2H_2O$ powders having Fe to Mn mixing ratios of 9:1, 8:2, 7:3, 6:4, 5:5 with a $MnSO_4{\cdot}4H_2O$ solution. The thermal decomposition of synthesized $Fe_{1-x}Co_xC_2O_4{\cdot}2H_2O$ and $Fe_{1-x}Mn_xC_2O_4{\cdot}2H_2O$ was analyzed in an Ar atmosphere with TG/DTA. The synthesized powders were heat-treated for 3 hours in an Ar atmosphere at $450^{\circ}C$ to produce activated powders of $(Fe_{1-x}Co_x)_3O_{4-{\delta}}$ and $(Fe_{1-x}Mn_x)_3O_{4-{\delta}}$. The activated powders were reacted with a mixed gas (Ar : 85 %, $CO_2$ : 15 %) at $300^{\circ}C$ for 12 hours. The exhaust gas was analyzed for $CO_2$ with a $CO_2$ gas analyzer. The decomposition of $CO_2$ was estimated by measuring $CO_2$ content in the exhaust gas after the reaction with $CO_2$. For $(Fe_{1-x}Mn_x)_3O_{4-{\delta}}$, the amount of $Mn^{2+}$ oxidized to $Mn^{3+}$ increased as x increased. The ${\delta}$ value and $CO_2$ decomposition efficiency decreased as x increased. When the ${\delta}$ value was below 0.641, $CO_2$ was not decomposed. For $(Fe_{1-x}Co_x)_3O_{4-{\delta}}$, the ${\delta}$ value and $CO_2$ decomposition efficiency increased as x increased. At a ${\delta}$ value of 0.857, an active state was maintained even after 12 hours of reaction and the amount of decomposed $CO_2$ was $52.844cm^3$ per 1 g of $(Fe_{0.5}Co_{0.5})_3O_{4-{\delta}}$.

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

• Journal of Magnetics
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• v.21 no.1
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• pp.40-45
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• 2016

Nickel substituted nano-sized ferrite powders, $Co_{1-x}Ni_xFe_2O_4$, $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$), were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently compared. The lattice constants decreased as quantity of nickel substitution increased, while the particle size decreased in $Co_{1-x}Ni_xFe_2O_4$ ferrite but increased for the $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites. For the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$) ferrite powders, the $M{\ddot{o}}ssbauer$ spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of $Mn_{0.8}Zn_{0.1}Ni_{0.1}Fe_2O_4$ consisted of two Zeeman sextets and one single quadrupole doublet due to the ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explain the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. The saturation magnetization decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. The coercivity decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. These variations could thus be explained by using the site distribution equations, particle sizes and spin magnetic moments of the substituted ions.

• Journal of Magnetics
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• v.11 no.1
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• pp.51-54
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• 2006

Variation of magnetic properties through Cr substitution for Co in inverse-spinel $CoFe_2O_4$ has been investigated by vibrating-sample magnetometry (VSM) and conversion electron $M\ddot{o}ssbauer$ spectroscopy (CEMS). $Cr_{x}Co_{1-x}Fe_2O_4$ samples were prepared as thin films by a sol-gel method. The lattice constant of the $Cr_{x}Co_{1-x}Fe_2O_4$ samples was found to remain unchanged, explainable in terms of a reduction of tetrahedral $Fe^{3+}$ ion to $Fe^{2+}$ due to substitution of $Cr^{3+}$ ion into octahedral $Co^{2+}$ site. The existence of the tetrahedral $Fe^{2+}$ ions in $Cr_{x}Co_{1-x}Fe_2O_4$ was confirmed by CEMS analysis. Room-temperature magnetic hysteresis curves for the $Cr_{x}Co_{1-x}Fe_2O_4$ films measured by VSM revealed that the saturation magnetization $M_s$ increases by Cr doping. The $M_s$ is maximized when x = 0.1 and decreases for higher x but is still bigger than that of $CoFe_2O_4$. The increase of $M_s$ can be explained partly by the reduction of the tetrahedral $Fe^{3+}$ ion to $Fe^{2+}$.

• Journal of the Korean Chemical Society
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• v.37 no.7
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• pp.648-654
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• 1993

$[M(cyclam)X_2]Y(M=Co^{3+},\;Fe^{3+},\;Mn^{3+}\;:\;X=Cl-^,\;Br^-,\;NCS^-\;:\;Y=Cl^-,\;Br^-,\;NCS^-),\;[Co(trans-14-diene)X_2]Y(X=Cl^-,\;Br^-\;:\;Y=ClO_4^-)\;and\;[Co(trans-14-diene)](ClO_4)_2$ were able to activate an molecular oxygen under sodium borohydride. 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol reacted with activated molecular oxygen to give 2,4-tert-butyl-1,6-benzoquinone(BQ) and 3,5,3',5'-tetra-tert-butyldiphenoquinone(DPQ). The saturated tetraazamacrocyclic complexes, $[Co(cyclam)X_2]Y$, were more an effective catalyst than $[Co(trans-14-diene)X_2]Y$ the unsaturated complexes in the formation of BQ and DPQ. The mole ratio of $O_2$ vs. catalyst $(O_2/M)$ for $[Co(cyclam)X_2]Y$ and [Co(trans-14-diene)X_2]Y$ was 1/1, while it was 1/2 for $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$. The results suggested that Co(III)-macrocyclic complexes activated molecular oxygen as superoxolike ${O_2}^-$ and $[M(cyclam)Cl_2]Cl(M=Fe(III),\;Mn(III))$ activated that as peroxolike $O_2^{2-}$.

• Journal of the Korean Magnetics Society
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• v.16 no.1
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• pp.1-5
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• 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 $Co^{3+}$.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1613-1618
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• 2014

Perovskite-type oxides are promising oxygen carriers in producing oxygen-enriched $CO_2$ gas stream for oxyfuel combustion. In this study, a new series of $SrCo_{1-x}Fe_xO_{3-{\delta}}$ (x = 0.2, 0.4, 0.6, 0.8) was prepared and used to produce $O_2/CO_2$ mixture gas. The phase, crystal structure, and morphological properties of $SrCo_{1-x}Fe_xO_{3-{\delta}}$ were investigated through X-ray diffraction, specific surface area measurements, and environmental scanning electron microscopy. The oxygen desorption performance of $SrCo_{1-x}Fe_xO_{3-{\delta}}$ was studied in a fixed-bed reactor system. Results showed that the different x values of $SrCo_{1-x}Fe_xO_{3-{\delta}}$ have no obvious effects on crystalline structure. However, the oxygen desorption performance of $SrCo_{1-x}Fe_xO_{3-{\delta}}$ is improved by Co doping. Moreover, $SrCo_{0.8}Fe_{0.2}O_{3-{\delta}}$ synthesized via a new EDTA method has a larger BET surface area ($40.396m^2/g$), smaller particle size (48.3 nm), and better oxygen production performance compared with that synthesized through a liquid citrate method.

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.543-553
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• 1996

Oxygen reduction in an alkaline fuel cell was studied by using perovskite type oxides as an oxygen electrode catalyst. The high surface area catalysts were prepared by malic acid method and had a formula of $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$(x=0.00, 0.01, 0.10, 0.20, 0.35 and 0.50). From the result of XRD pattern and specific surface area due to the amount of Fe substitution and the consumption of ammonia-water, the complex formation of Fe ion with $NH_3$ was the main factor for both the phase stability of perovskite and the increase of specific surface area. Multi-step calcination was necessary to give a single phase of perovskite in catalyst precursor. The crystal structure of the catalysts was simple cubic perovskite, which was verified from the XRD patterns of the catalysts. The activity of oxygen reduction was monitored by the techniques of cyclic voltammetry, static voltage-current method, and current interruption method. The activity(current density) of oxygen reduction showed its minimum at x=0.01 and its maximum between 0.20 and 0.35 of x-value in $La_{0.6}Sr_{0.4}Co_{1-x}Fe_xO_3$. This tendency was independent of the change of surface area.

• Journal of the Korean Magnetics Society
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• v.15 no.2
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• pp.109-112
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• 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 $Ti_{1-x}Fe_xO_{2-\delta}$.

• Proceedings of the Korean Magnestics Society Conference
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• 1992.10a
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• pp.50-51
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• 1992