• Applied Chemistry for Engineering
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• v.18 no.6
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• pp.618-624
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• 2007

thermochemical methane reforming consisting of two steps on Cu/Fe/Zr mixed oxide media was carried out using a fixed bed infrared reactor. In the first step, the metal oxide was reduced with methane to produce CO, $H_2$ and the reduced metal oxide in the temperature of 1173 K. In the second step, the reduced metal oxide was re-oxidized with steam to produce $H_2$ and the metal oxide in the temperature of 973 K. The reaction characteristics on the added amounts of Cu in Cu/Fe/Zr mixed oxide media and the cyclic tests were evaluated. With the increase of the added amount of Cu in Cu/Fe/Zr mixed oxide media, the conversion of $CH_4$, the selectivity of $CO_2$ and the $H_2/CO$ molar ratio were increased, while the selectivity of CO was decreased in the first step. On the other hand, the evolved amount of $H_2$ was decreased with increasing the added amount of Cu in the second step. The $Cu_xFe_{3-x}O_4/ZrO_2$ medium added with Cu of x = 0.7 showed good regeneration properties in the 10th cyclic tests indicating that the medium had high durability. In addition, the gasification of the deposited carbon in the water splitting step was promoted with the addition of Cu in the media.

• New & Renewable Energy
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• v.2 no.2 s.6
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• pp.69-74
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• 2006

본 연구는 페라이트의 Fe 양이온 일부를 Ni, Mn, Co등으로 치환하여 M-ferrite를 제조하여 열화학적 2단계 물 분해 반응의 특성을 비교 평가하였고, XRD, SEM, GC등의 분석으로 각 금속산화물의 특성을 확인하였다. M-ferrites 는 고상법으로 제조하였다. 각각의 M-ferrite에 대한 열적환원은 1573K 에서 진행하였고 물 분해 반응은 1273K 에서 실시하였다. 이 반응에서 생성된 가스는 전량 포집하여 GC를 통해 분석하였다. 반응 전후의 시료에 대하여 SEM, XRD를 분석하여 GC결과와 함께 금속산화물의 산화환원반응 특성을 고찰하였다. 그 결과로서 물 분해 반응 후 M-ferrite (M=Co, Ni, Mn)의 생성을 XRD를 통하여 확인할 수 있었고, 물 분해 반응과의 비교결과 격자상수의 증대가 M-ferrite내의 산소의 환원에 영향을 미치는 것을 알 수 있었다. SEM결과에서는 4cycle의 물 분해 반응 후 Mn-ferrite의 심한 sintering 현상을 확인 할 수 있었다.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.43-46
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• 2006

본 연구는 페라이트의 Fe 양이온 일부를 Ni, Mn, Co등으로 치환하여 M-ferrites를 제조하여 열화학적 2단계 물 분해 반응의 특성을 비교 평가하였고, XRD, SEM, GC등의 분석으로 각 금속산화물의 특성을 확인하였다. M-ferrites는 고상법으로 제조하였다. 각각의 M-ferrites에 대한 열적환원은 1573K에서 진행하였고 물 분해 반응은 1273K에서 실시하였다. 이 반응에서 생성된 가스는 전량 포집하여 GC를 통해 분석하였다. 반응 전후의 시료에 대하여 SEM, XRD를 분석하여 GC결과와 함께 금속산화물의 산화환원반응 특성을 고찰하였다. 그 결과로서 물 분해 반응 후 M-ferrite (M=Co, Ni, Mn)의 생성을 XRD를 통하여 확인할 수 있었고, 물 분해 반응과의 비교결과 격자상수의 증대가 M-ferrite내의 산소의 환원에 영향을 미치는 것을 알 수 있었다. SEM결과에서는 4cycle의 물 분해 반응 후 Mn-ferrite의 심한 sintering 현상을 확인 할 수 있었다.

• Journal of the Korean Solar Energy Society
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• v.33 no.3
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• pp.42-50
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• 2013

Solar thermal reactor was studied for hydrogen production with a two step thermochemical cycle including T-R(Thermal Reduction) step and W-D(Water Decomposition) step. NiFe2O4 and Fe3O4 supported by monoclinic ZrO2 were used as a catalyst device and Ni powder was used for decreasing the T-R step reaction temperature. Maintaining a temperature level of about $1100^{\circ}C$ and $1400^{\circ}C$, for 2-step thermochemical reaction, is important for obtaining maximum performance of hydrogen production. The controller was designed for adjusting high temperature solar thermal energy heating the foam-device coated with nickel- ferrite powder. A Pill temperature control system was designed based on 2-step thermochemical reaction experiment data(measured concentrated solar radiation and the temperature of foam device during experiment). The cycle repeated 5 times, ferrite conversion rate are 4.49~29.97% and hydrogen production rate is 0.19~1.54mmol/g-ferrite. A temperature controller was designed for increasing the number of reaction cycles related with the amount of produced hydrogen.

• Journal of Energy Engineering
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• v.15 no.2 s.46
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• pp.107-117
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• 2006

The status of water splitting thermochemical cycle for hydrogen production was reviewed in this article. Mass production of hydrogen could be possible using the thermochemical process which is similar to the concept of conventional chemical reaction system if the high temperature heat source is available. The mediators (chemicals and reagents) should be used to split chemically stable water, and should be recycled in a closed cycle in order to be environmentally acceptable. Though there is no process to reach commercial stage, IS cycle, two-step cycles based on metallic oxide such as ZnO/Zn, $Fe_3O_4/FeO$ and the associated cycles are attracted due to their possibilities of application. Development of materials for high temperature and/or corrosive conditions during thermochemical process is still important topic in some thermochemical processes.

• Journal of Hydrogen and New Energy
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• v.18 no.2
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• pp.109-115
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• 2007

Solar energy conversion to hydrogen was carried out via a two-step thermochemical water splitting using metal oxide redox pair. To simulate the solar radiation, a 7 kW short arc Xe-lamp was used. Partially reduced iron oxide and cerium oxide have the water splitting ability, respectively. So, $Fe_3O_4$ supported on $CeO_2$ was selected as the active material. $Fe_3O_4/CeO_2$(20 wt/80 wt%) was prepared by impregnation method, then the active material was washcoated on the ceramic honeycomb monolith made of mullite and cordierite. Oxygen was released at the reduction step($1673{\sim}1823\;K$) and hydrogen was produced from water at lower temperature($873{\sim}1273\;K$). The result demonstrate the possibility of the 2-step thermochemical water splitting hydrogen production by the active material washcoated monolith. And hydrogen and oxygen was produced separately without any separation process in a monolith installed reactor. But the SEM and EDX analysis results revealed that the support used in this experiment is not suitable due to the thermal instability and coating material migration.

• Journal of the Korean Vacuum Society
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• v.20 no.5
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• pp.374-380
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• 2011

Carbon coils could be synthesized on nickel catalyst layer-deposited silicon oxide substrate using $C_2H_2$ and $H_2$ as source gases and $SF_6$ as an additive gas under thermal chemical vapor deposition system. The characteristics (formation density and morphology) of as-grown carbon coils according to the injection stage of $SF_6$ gas incorporation were investigated. A continuous injecting of $SF_6$ gas flow could give rise to many types of carbon coils-related geometries, namely linear tub, micro-sized coil, nano-sized coil, and wave-like nano-sized coil. However, the limitation of the geometry as the nano-sized geometries of carbon coils could be achieved by the incorporation of $SF_6$ in a short time (1 min) during the initial deposition stage. A delayed injection of a short time $SF_6$ gas flow can deteriorate the limitation of the geometries. It confirms that the injection time and its starting point of $SF_6$ gas flow would be very important to determine the geometries of carbon coils.

• Journal of Hydrogen and New Energy
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• v.19 no.6
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• pp.505-513
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• 2008

The two-step thermochemical cycle was examined on the $CeO_2$, YSZ, and $ZrO_2$-supported $NiFe_2O_4$ to investigate the effects of support material addition. The supported $NiFe_2O_4$ was prepared by the aerial oxidation method. Thermal reduction was conducted at 1573K and 1523K while water-splitting was carried out at 1073K. Supporting $NiFe_2O_4$ on $CeO_2$, YSZ and $ZrO_2$ alleviated the high-temperature sintering of iron-oxide. As a result, the supported $NiFe_2O_4$ exhibited greater reactivity and repeatability in the water-splitting cycle as compared to the unsupported $NiFe_2O_4$. Especially, $ZrO_2$-supported $NiFe_2O_4$ showed better sintering inhibition effect than other supporting materials, but hydrogen production amount was decreased as cycle repeated. In case of $CeO_2$-supported $NiFe_2O_4$, improvement of hydrogen production was found when the thermal reduction was conducted at 1573K. It was deduced that redox reaction of $CeO_2$ activated above 1573K.

• Korean Journal of Materials Research
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• v.11 no.8
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• pp.641-646
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• 2001

The $CoSi_2$ layers have been in-situ grown on undoped poly-Si by the reactive chemical vapor deposition of $Co({\Eta}^5-C_5H_5)(CO)_2$ at $650^{\circ}C$ and their thermal stabilities have been investigated in the temperature range of 800 to $1000^{\circ}C$. The $CoSi_2$ layer grown by the in-situ method had grains with large area of (111) plane, while grains with little area of (111) plane appeared on the $CoSi_2$ layer grown by the conventional two-step method where $CoSi_2$ formed first and transformed to $CoSi_2$. The thermal stability of the $CoSi_2$ layer grown by the in- situ process was improved by more than $100^{\circ}C$ higher than that of the $CoSi_2$ layer grown by the conventional two-step process. The $CoSi_2$ layer grown in situ on a large-grained Poly-Si was stable up to $950^{\circ}C$. The effect of stability improvement by the in situ growth was more pronounced when the grain sizes of the poly-Si substrate were small. The improved thermal stability of the in-situ grown $CoSi_2$ layer could be mainly due to the formation of a uniform $CoSi_2$ layer with the $CoSi_2$ grains, which are in the form of epitaxial-like growth on the each poly-Si grains, causing a reduction of the interfacial energy of the system.