Activated magnetite (Fe3O4-δ) has the capability of decomposing CO2 proportional to the δ-value at comparativelylow temperature of 300oC. To enhance the CO2 decomposition capability of Fe3O4-δ, (Fe1-xCox)3O4-δ and (Fe1-xMnx)3O4-δ weresynthesized and then reacted with CO2. Fe1-xCoxC2O4·2H2O powders having Fe to Co mixing ratios of 9:1, 8:2, 7:3, 6:4, and5:5 were synthesized by co-precipitation of FeSO4·7H2O and CoSO4·7H2O solutions with a (NH4)2C2O4·H2O solution. The samemethod was used to synthesize Fe1-xMnxC2O4·2H2O powders having Fe to Mn mixing ratios of 9:1, 8:2, 7:3, 6:4, 5:5 with aMnSO4·4H2O solution. The thermal decomposition of synthesized Fe1-xCoxC2O4·2H2O and Fe1-xMnxC2O4·2H2O was analyzedin an Ar atmosphere with TG/DTA. The synthesized powders were heat-treated for 3 hours in an Ar atmosphere at 450oCto produce activated powders of (Fe1-xCox)3O4-δ and (Fe1-xMnx)3O4-δ. The activated powders were reacted with a mixed gas(Ar:85%, CO2:15%) at 300oC for 12 hours. The exhaust gas was analyzed for CO2 with a CO2 gas analyzer. The decom-position of CO2 was estimated by measuring CO2 content in the exhaust gas after the reaction with CO2. For (Fe1-xMnx)3O4-δ,the amount of Mn2+ oxidized to Mn3+ increased as x increased. The δ value and CO2 decomposition efficiency decreased asx increased. When the δ value was below 0.641, CO2 was not decomposed. For (Fe1-xCox)3O4-δ, the δ value and CO2decomposition efficiency increased as x increased. At a δ value of 0.857, an active state was maintained even after 12 hoursof reaction and the amount of decomposed CO2 was 52.844cm3 per 1g of (Fe0.5Co0.5)3O4-δ.

LiMn2O4 catalyst for CO2 decomposition was synthesized by oxidation method for 30 min at 600℃ in an electric furnace under air condition using manganese(II) nitrate (Mn(NO3)2·6H2O), Lithium nitrate (LiNO3) and Urea (CO(NH2)2). The synthesized catalyst was reduced by H2 at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then CO2 decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after CO2 decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by H2, the phase of LiMn2O4 catalyst was transformed into Li2MnO3 and Li1-2δMn2-δO4-3δ-δ' of tetragonal spinel phase. After CO2 decomposition reaction, it was confirmed that the peak of LiMn2O4 of spinel phase. The optimal reduction temperature of the catalyst with H2 was confirmed to be 450℃(maximum weight-increasing ratio 9.47%) in the case of LiMn2O4 through the TGA analysis. Decomposition rate(%) using the LiMn2O4 catalyst showed the 67%. The crystal structure of the synthesized LiMn2O4 observed with a scanning electron microscope(SEM) shows cubic form. After reduction, LiMn2O4 catalyst became condensed each other to form interface. It was confirmed that after CO2 decomposition, crystal structure of LiMn2O4 catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and CO2 decomposition ; Li2MnO3 and Li1-2δMn2-δO4-3δ-δ' of tetragonal spinel phase at the first time of CO2 decomposition appear like the same as the above contents. Phase-transition at 2~5 time ; Li2MnO3 and Li1-2δMn2-δO4-3δ-δ' of tetragonal spinel phase by reduction and LiMn2O4 of spinel phase after CO2 decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2~5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of CO2. That is to say, at the first time, it showed 67% in CO2 decomposition rate and after 5 times reaction of CO2 decomposition, it showed 67% nearly the same as the first time.

The spinel Fe3O4 powders were synthesized using 0.2 M-FeSO4·7H2O and 0.5 M-NaOH by oxidation in air and the spinel LiMn2O4 powders were synthesized at 480 ℃ for 12 h in air by a sol-gel method using manganese acetate and lithium hydroxide as starting materials. The synthesized LiMn2O4 powders were mixed at portion of 5, 10, 15 and 20 wt% of Fe3O4 powders using a ball-mill. The mixed catalysts were dried at room temperature for 24 hrs. The mixed catalysts were reduced by hydrogen gas at 350 ℃ for 2 h. The carbon dioxide decomposition rates of the mixed catalysts were 90% in all the mixed catalysts but the decomposition rate of carbon dioxide was increased with adding LiMn2O4 powders to Fe3O4 powders.

The spinel LiMn2O4 powders were synthesized at 480℃ for 12 h in air by a sol-gel method using manganese acetate and lithium hydroxide as starting material and the Fe3O4 powders were synthesized by the precipitation method using 0.2M-FeSO4·H2O and 0.5M-NaOH. The synthesized Fe3O4 powders were mixed at portion of 5, 10, 15 and 20 wt% about LiMn2O4 powders through ball-milling followed by drying at room temperature for 48 h in air. The mixed catalysts were reduced at 350℃ for 3 h by hydrogen and the decomposition rate of carbon dioxide was measured at 350℃ using the reduced catalysts. As the results of CO2 decomposition experiments, the decomposition rates of carbon dioxide were 85% in all catalysts but the initial decomposition rates of CO2 were slightly high in the case of the 5%-Fe3O4 added catalyst.

산소 결핍 페라이트 (oxygen deficient ferrites, ODF) MeFe2O4-δ는 약 300˚C의 낮은 온도에서 CO2를 C와 O2로 분해한다. 본 연구에서는 (Nix, Zn1-xFe24 초미세 페라이트 분말을 수열합성법으로 제조하여 CO2 분해특성을 살펴보았다. 제조된 페라이트는 XRD 분석 결과, 페라이트의 전형적인 스피넬 구조를 보여주고 있으며, ICP-AES, EDS 정량분석에 의하여 초기 혼합 조성비와 거의 동일한 조성비로 합성되었음을 알 수 있었다. 제조된 (Ni, Zn)-ferrites 분말의 BET 비표면적은 약 110mg2/g 이상의 큰 값으로 나타났으며, 입자크기는 약 5~10nm로 매우 작았다. 산소결핍 페라이트 (Nix, Zn1-x)Fe2O4-δ</TEX>의 CO2 분해 효율은 조성에 따라 큰 차이를 보이지 않았으며 3원계 (Ni, Zn)-ferrite가 Ni-ferrite보다 더 높았다.

CuxFe3-xO4 catalyst and ZnxFe3-xO4 catalyst were synthesized by the air oxidation method with various C(II) and Zn(II) weights. Activated catalysts decomposed carbon dioxide to carbon at 350℃, 380℃, 410℃ and 440℃. The value of carbon dioxide decomposition rate for Cu0.003Fe2.997O4 and Zn0.003Fe2.997O4 catslysts than was better catalysts. The decomposed rate of the catalysts is about 85%~90%. The reaction rate constant(4.00 psi1-α/min) and activation energy(2.62 kcal/mole) of Cu0.003Fe2.997O4 catalyst are better than Zn0.003Fe2.997O4