• Journal of the Korean Solar Energy Society
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• v.37 no.2
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• pp.13-22
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• 2017

Two-step water splitting thermochemical cycle with $CeO_2/ZrO_2$ foam device was investigated by using a solar simulator composed of 2.5 kW Xe-Arc lamp and mirror reflector. The hydrogen production of $CeO_2/ZrO_2$ foam device depending on heat recovery of Thermal-Reduction step and Water-Decomposition step was analyzed, and the hydrogen production of $CeO_2/ZrO_2$ and $NiFe_2O_4/ZrO_2$ foam devices was compared. Resultantly, the quantity of hydrogen generation increased by 52.02% when the carrier gas of Thermal-Reduction step is preheated to $200^{\circ}C$ and, when the $N_2/steam$ is preheated to $200^{\circ}C$ in the Water-Decomposition step, the quantity of hydrogen generation increased by 35.85%. Therefore, it is important to retrieve the heat from the highly heated gases discharged from each of the reaction spaces in order to increase the reaction temperature of each of the stages and thereby increasing the quantity of hydrogen generated through this.

• 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.

• 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.

• Nuclear Engineering and Technology
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• v.53 no.6
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• pp.2066-2073
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• 2021

The use of nuclear reactors is a large studied possible solution for thermochemical water splitting cycles. Nevertheless, there are several problems that have to be solved. One of them is to increase the efficiency of the cycles. Hence, in this paper, a thermal energy optimization of a Sulfur-Iodine nuclear hydrogen production cycle was performed by means a heuristic method with the aim of minimizing the energy targets of the heat exchanger network at different minimum temperature differences. With this method, four different heat exchanger networks are proposed. A reduction of the energy requirements for cooling ranges between 58.9-59.8% and 52.6-53.3% heating, compared to the reference design with no heat exchanger network. With this reduction, the thermal efficiency of the cycle increased in about 10% in average compared to the reference efficiency. This improves the use of thermal energy of the cycle.

• Journal of Hydrogen and New Energy
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• v.19 no.4
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• pp.305-312
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• 2008

ZnO/Zn redox cycle is the one of the promising thermochemical cycles for hydrogen production via water splitting with high temperature heat source like a concentrated solar energy. This paper reports the particle size effect of Zinc on water splitting behavior. Water splitting reaction experiments were carried out at isothermal conditions of 350 and 400$^{\circ}C$ in TGA (Thermo Gravimetric Analyzer) using four commercial Zinc powders (nano, <10 ${\mu}m$, <150 ${\mu}m$ and $150{\sim}600\;{\mu}m$ particle sizes). Before the experiments, average particle size of Zinc powders was analyzed by PSA (Particle Size Analysis). After the experiments, XRD (X-Ray Diffraction) and SEM (Scanning Electron Microscope) analyses were conducted on the samples. The experimental results showed that particle size had a effect on the conversion of Zinc to ZnO. Zinc conversion was increased, as the particle size decreased. Especially, the nano size particles were aggregated and the particle's morphology changed on the surface during hydrolysis reaction.

• Journal of Hydrogen and New Energy
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• v.15 no.1
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• pp.32-38
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• 2004

Thermal behaviors of $(Cu_{0.5}Mn_{0.5})Fe_2O_4$, prepared by a solid method, were investigated for $H_2$ production by a thermochemical cycle. The thermal reduction of $(Cu_{0.5}Mn_{0.5})Fe_2O_4$ started from $300^\circ{C}$ and the weight loss was 1.3 wt% up to 1200. XRD shows the prepared ferrite has the spinel structure with a lattice constant of $8.414{\AA}$ and changed to the oxygen deficient structure by thermal reduction. Oxygen and hydrogen can be separately produced by the cycles of thermal reduction and water oxidation of the oxygen deficient ferrite.

• Journal of Hydrogen and New Energy
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• v.17 no.4
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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.

• Journal of Hydrogen and New Energy
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• v.12 no.3
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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.

• Journal of Hydrogen and New Energy
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• v.22 no.1
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• pp.13-20
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• 2011

$SO_2$ has been absorbed and separated selectively by an ionic liquid from $SO_2/O_2$ mixture decomposed from sulfuric acid during the thermochemical SI cycle for the water splitting. In order to design and operate high pressure $SO_2/O_2$ separation system, the solubility of $SO_2$ in [EMIm]$EtSO_4$ (1-ethyl-3-methylimidazolium ethylsulfate) has been measured by Magnetic Suspension Balance at high pressure and temperature. Based on the measured solubility, a pressurized separation system was set up and operated. 194 L/h of $SO_2$($SO_2:O_2$=0.65:1) has been separated with 99.85% of $O_2$ at the vent of absorption tower, which is 22.7% of the theoretically ideal capacity of the system. This discrepancy results from the reduced contact between the gaseous $SO_2$ and the ionic liquid. Increased $SO_2$ supply, scale-up of the absorption column, and a faster ionic liquid circulation speed were suggested to improve the separation capacity.

• Journal of the Korean Solar Energy Society
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• v.33 no.2
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• pp.93-100
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• 2013

Two-step thermochemical cycle using ferrite-oxide($Fe_2O_4$) 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. And cerium oxide($CeO_2$) device was used for increasing $H_2$ production rate. $CeO_2$ device had low thermal resistance, however, more $H_2$ production rate than $Fe_2O_4$ device.