• 한국수소및신에너지학회논문집
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• 제17권4호
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• pp.353-361
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• 2006

As one of the thermochemical water splitting hydrogen production cycles, which could be operated at the lower temperature below 1200 K, we investigated the feasibility of the cyclic operation of Ispra Mark 2 cycle with the addition of $ZrO_2$. The cycle is theoretically composed of three reaction steps; (1) 1st step($2MnO_2{\rightarrow}Mn_2O_3+0.5O_2$), (2) 2nd step($Mn_2O_3+4NaOH{\rightarrow}2Na_2O{\cdot}MnO_2+H_2+H_2O$) and (3) 3rd step($2Na_2O{\cdot}MnO_2H_2O{\rightarrow}4NaOH+2MnO_2$). From the TPR tests, the temperature ranges for $O_2$ production in 1st step and $H_2$ production in 2nd step were $550{\sim}750^{\circ}C$ and $650{\sim}750^{\circ}C$, respectively. In $MnO_2/Mn_2O_3/NaOH$ system, the formation of molten products due to the reaction between manganese oxides and NaOH were greatly decreased with the addition of $ZrO_2$. In addition, the results of a cyclic test were discussed with the viewpoint of $H_2$ production amounts and the feasibility of the process improvement.

• JSTS:Journal of Semiconductor Technology and Science
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• 제14권1호
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• pp.92-95
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• 2014

In this work we have synthesized ZnS:Mn nanocrystals (NCs) using a simple one step thermochemical method. $Zn(NO_3)_2$ and $Na_2S_2O_3$ were used as the precursors and $Mn(NO_3)_2$ was the source of impurity. Thioglycolic acid (TGA) was used as the capping agent and the catalyst of the reaction. The structure and optical property of the NCs were characterized by means of X- ray diffraction (XRD), HRTEM, UV-visible optical spectroscopy and photoluminescence (PL). X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses demonstrated cubic phase ZnS:Mn NCs with an average size around 3 nm. Synthesized NCs exhibited band gap of about 4 eV. Photoluminescence spectra showed a yellow-orange emission with a peak located at 585 nm, demonstrating the Mn incorporation inside the ZnS particles.

• 한국수소및신에너지학회논문집
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• 제12권3호
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• pp.219-229
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• 2001

Hydrogen production by a 2-step water-splitting thermochemical cycle using metal oxides (ferrites) redox pairs and $CH_4$ have been studied in this experiment. The ferrites were reacted with $CH_4$ at $700{\sim}800^{\circ}C$ to produce CO, $H_2$ and various reduced phases (reduction step); these were then reoxidized with water vapor to generate $H_2$ in water-splitting step (oxidation step) at $600{\sim}700^{\circ}C$. The reduced ferrites, Ni-FeO and Ni-Fe alloy showed respectively different reactivity for $H_2$ formation from $H_2O$. In reduction reaction at $800^{\circ}C$, carbon was deposited on surface of Ni-ferrite due to $CH_4$ decomposition. This reduced phase containing carbon, which was taken quite different feature from other phase, produced $H_2$, CO, $CO_2$ by reacting with $H_2O$ at $600^{\circ}C$. The amount of $H_2$ evolved using reduced phase containing carbon was much higher than that of other phase.

• 공업화학
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• 제18권6호
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• pp.618-624
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• 2007

Cu/Fe/Zr 혼합 산화물 매체 상에서의 2단계 열화학 메탄 개질 반응을 고정층 적외선 반응로를 이용하여 수행했다. 첫 번째 단계에서 금속 산화물은 CO, $H_2$ 및 환원된 금속 산화물을 생성하기 위하여 1173 K의 온도에서 메탄으로 환원되었다. 두번째 단계에서 환원된 금속 산화물은 $H_2$와 금속 산화물을 생성하기 위하여 973 K의 온도에서 재산화되었다. 본 연구에서는 Cu/Fe/Zr 혼합 산화물 내 Cu 첨가량에 따른 반응 특성과 사이클 반응을 평가하였다. Cu/Fe/Zr 혼합 산화물 매체 내 Cu 첨가량 증가에 따라 첫 번째 단계에서 $CH_4$ 전환율, $CO_2$로의 선택성 및 $H_2/CO$ 몰 비는 증가하였으며, CO로의 선택성은 감소하는 경향을 나타냈다. 한편, 두 번째 단계에서 $H_2$ 생성량은 Cu 첨가량 증가에 따라 감소하는 것으로 나타났다. Cu의 첨가량이 x = 0.7인 $Cu_xFe_{3-x}O_4/ZrO_2$ 매체는 내구성이 우수한 매체임을 지시하듯이 10회의 사이클 순환 반응에서 우수한 재생 성능을 나타냈다. 더 나아가 물 분해 단계에서 침적된 탄소의 가스화 반응은 매체 내 Cu 첨가에 의해 촉진되었다.

• 에너지공학
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• 제15권2호
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• pp.107-117
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• 2006

물을 분해하여 수소를 만드는 방법으로서 열화학싸이클을 이용한 방법에 대하여 그동안의 연구 동향에 대하여 살펴보았다. 수소생산이란 관점에서 열화학싸이클이 갖는 장점은 일정한 고온의 열을 얻을 수 있다면, 반응속도의 향상과 아울러 대용량화가 가능하다는 점이다. 안정한 물을 분해하려면 물의 산화/환원이 용이한 매개체를 써서 수소 및 산소를 발생하게 하고 순환시키게 되는데, 매개체가 유독성 물질이라면 이 과정에서 누출이 되지 않도록 하여야 한다. 아직 상용화단계에는 미치지 못하였지만, 일본, 스위스, 이스라엘, 미국, 한국 등에서 집중적으로 연구되고 있는 내용은 IS 싸이클과 ZnO/Zn, $Fe_3O_4/FeO$등과 같은 금속산화물계를 이용한 싸이클들이며, 고온용 및 내부식성 소재와 시스템 분야에서 아직 해결해야할 점이 많다.

• 한국수소및신에너지학회논문집
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• 제13권3호
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• pp.249-258
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• 2002

Thermochemical water-splitting IS(Iodine-Sulfur) process has been investigating for large-scale hydrogen production. For the construction of an efficient process scheme, two kinds of membrane technologies are under investigating to improve the hydrogen producing HI decomposition step. One is a concentration of HI in quasi-azeotropic HIx ($HI-H_2O-I_2$) solution by elecro-electrodialysis. It was confirmed that HI concentrated from the $HI-H_2O-I_2$ solution with a molar ratio of 1:5:1 at $80^{\circ}C$. The other is a membrane reactor to enhance the one-pass conversion of thermal decomposition reaction of gaseous hydrogen iodide (HI). It was found from the simulation study that the conversion of over 0.9 would be attainable using the membrane reactor using the gas permeation properties of the prepared silica hydrogen permselective membrane by chemical vapor deposition (CVD). Design criterion of the membrane reactor was also discussed.

• 한국수소및신에너지학회논문집
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• 제19권6호
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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.

• 한국태양에너지학회 논문집
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• 제31권1호
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• pp.107-114
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• 2011

Two-step thermochemical cycle using ferrite-oxide($Fe_3O_4$) device was investigated. The $H_2O$(g) was converted into $H_2$ in the first experiment which was performed using a dish type solar thermal system. However the experiment was lasted only for 2 cycles because the metal oxide device was sintered and broken down. Another problem was that the reaction was taken place mainly on a side of the metal oxide device. The $m-ZrO_2$, which was widely known as a material preventing sintering, was applied on the metal oxide device. The ferrite loading rate and the thickness of the metal oxide device were increased from 10.67wt% to 20wt% and from 10mm to 15mm, respectively. The chemical reactor having two inlets was designed in order to supply the reactants uniformly to the metal oxide device. The second-experiment was lasted for 5 cycles, which was for 6 hours. The total amount of the $H_2$ production was 861.30mL.