• Journal of the Korean Ceramic Society
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• v.54 no.1
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• pp.1-8
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• 2017

Electrochemical water splitting to produce hydrogen energy is regarded as a promising energy conversion process for its environmentally friendly nature. To improve cell efficiency, the development of efficient water oxidation catalysts is essentially demanded. For several decades, 3d transition metal oxides have been intensively investigated for their high activity, good durability and low-cost. This review covers i) recent progress on 3d transition metal oxide electrocatalysts and ii) the reaction mechanism of oxygen evolving catalysis, specifically focused on the proposed pathways for the O-O bond formation step.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.3
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• pp.189-198
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• 2008

Cooperative effects of Rh, Ce and Zr added to Fe-based oxide mediums were investigated using temperature programmed redox reaction (TPR/TPO) and isothermal redox reaction in the view point of hydrogen storage and release. As the results of TPR/TPO, Rh was a sale additive to remarkably promote the redox reaction on the medium as evidenced by the lower highest peak temperature, even though its addition was to accelerate deactivation of the mediums due to sintering. On the other hand, Ce and Zr additives played an important role to suppress deactivation of the medium in repeated redox cycles. The medium co-added by Rh, Ce and Zr (FRCZ) exhibited synergistic performance in the repeated isothermal redox reaction, and the amount of hydrogen produced in the water splitting step at 623 K was highly maintained at ca. $17\;mmol{\cdot}g^{-1}-Fe$ during three repeated redox cycles.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.272-272
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• 2013

The attractive features of photosynthetic reaction center proteins for energy application make them useful in solar energy conversion to hydrogen fuel or electrical energy. Almost unity charge separation quantum yield and its rapid speed of ~1ns, absorbance region in visible light (480~740 nm) and high proportion of photosynthetically active solar energy of 48.5% allowed photosystem1 to exploited as a bio-material for photo-energy devices. Directionality of photosystem1 in electron transfer can solve main problem in two-step water splitting process where back reaction deteriorates the overall efficiency. In the study, photosystem1 was extracted from spinach and the photo-induced excited electron in the reaction center was utilized in various field of light energy application. First, hydrogen evolving system realized by photodeposition of platinum at the end of the electron transfer chain, with combining specific semiconductor to oxidize water in the first step of Z-scheme. The evaluation by gas-chromatography demonstrated hydrogen evolution through the system. For the further application of photoelectrical material on electrode, photosystem1 have been controlled by copper ion, which is expected to assemble photosystem in specific orientation followed by maximized photoelectrical ability of film. The research proposed concrete methods for combining natural protein and artificial materials in one system and suggested possibility of designing interface between biological and inorganic materials.

• Transactions of the Korean hydrogen and new energy society
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• v.16 no.1
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• pp.49-57
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• 2005

[ $MO/Al_2O_3-ZrO_2$ ](M=Ni and Cu) mixed metal oxides were prepared using sol-gel method in order to investigate the applicability to the 2-step thermo-chemical water splitting process and their redox behaviors were studied by temperature programmed reaction(TPR) from room temperature to 900$^{\circ}C$ under 5% $H_2$/Ar for the reduction and $H_2O$/Ar for the oxidation, respectively. From the results, peaks of the reduction and the oxidation on temperature were shifted with the change of crystalline phases due to the addition of $Al_2O_3$ and $ZrO_2$. The intensities of the peaks were also increased with the increase of contents of NiO or CuO that could be considered as active species. In addition, based on the observation of SEM images before and after the redox test, it seemed that $Al_2O_3-ZrO_2$ added prevented high temperature sintering of active metal components such as Ni (or Cu) on the surface and played a role of dispersing the active species homogeneously in solid solution of mixed oxides.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.5
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• pp.394-402
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• 2008

The Effects of Cu or Ni additives co-added with Ce/Zr mixed oxides to Fe-based oxide mediums were investigated for the purpose of the replacement of Rh, a precious metal additive, in terms of hydrogen storage(reduction by hydrogen) and release(water splitting). From the results of temperature programmed reduction(TPR), initial reduction rate of iron oxide in the mediums was greatly increased with the addition of Cu, similar to that of Rh. For isothermal redox reaction of 10 cycles, the total amounts of hydrogen evolved in water splitting steps for the mediums added with Cu or Ni were highly maintained at ca. 7 mmol/g-material, even though the oxidation rates were slightly lower than that for the medium added with Rh. This result suggests that the replacement of Rh to Cu or Ni is possible as a co-additive for Fe-based oxide mediums.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.5
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• pp.616-624
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• 2011

Hydrogen storage and release of Fe/Zr/Mo mixed oxide mediums were investigated by hydrogen reduction and water splitting oxidation($Fe_3O_4+4H_2{\rightleftharpoons}3Fe+4H_2O$). As the results of TPR/O, Mo was an additive to enhance the reactivity of water splitting oxidation as well as the stability of the medium. On the other hand, it seemed that $ZrO_2$ additive provided the passway for the diffusion of gaseous chemicals on the medium in repeated redox cycles. Among the Fe/Zr/Mo mediums, a FeZrMo-7 medium (Fe/Zr/Mo=80/13/7mol%) exhibited the best performance with good durability during five repeated redox cycles. The amount of hydrogen evolved on the medium was maintained at ca. 10.7mmol-$H_2$/g-medium corresponding to the hydrogen storage amount of ca. 2.2wt%.

• Transactions of the Korean hydrogen and new energy society
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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 the Korean institute of surface engineering
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• v.51 no.6
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• pp.360-364
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• 2018

A facile method to fabricate freestanding CuO nanoleaves and CuO nanowires-based films was demonstrated. $Cu(OH)_2$ nanoleaves and nanowires were prepared by a hydrolysis reaction in aqueous solution including pyridine and NaOH with the tailored concentrations at room temperature. The films of freestanding CuO nanoleaves and CuO nanowires can be successfully obtained via the simple vacuum infiltration following a thermal dehydration reaction. The morphologies and crystallinity of the $Cu(OH)_2$ nanoleaves/nanowires and CuO nanoleaves/nanowires were characterized by XRD, SEM, TEM and FT-IR. The films fabricated with freestanding CuO nanoleaves and nanowires in this study may be applicable for building high-efficiency organic binder-free devices, such as gas sensors, batteries, photoelectrodes for water splitting and so on.

• Journal of Electrochemical Science and Technology
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• v.13 no.1
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• pp.54-62
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• 2022

The preparation of low-cost, simple, and scalable electrodes is crucial for the commercialization of water electrolyzers for H₂ production. Herein, we demonstrate the fabrication of cathodes through Mo-modified Zn phosphating of Ni foam (NiF) for water electrolysis, which has been largely utilized in surface coating industry. In situ growth of electrocatalytically active layers in the hydrogen evolution reaction (HER) was occurred after 1 min of phosphating to form ZnNiMoP_i, and subsequent thermal treatment and electrochemical activation resulted in the formation of ZnNiMoPO_xH_y. ZnNiMoPO_xH_y exhibited superior HER performance than NiF, primarily because of the increased electrochemically active surface area of ZnNiMoPO_xH_y compared to that of bare NiF. Although further investigations to improve the intrinsic electrochemical activity toward the HER and detailed mechanistic studies are required, these results suggest that phosphating is a promising coating method and will possibly advance the fabrication procedure of electrodes for water electrolyzers with better practical applications.

• Journal of the Korean institute of surface engineering
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• v.49 no.6
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• pp.521-529
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• 2016

In this study, titanium nanotubes, prepared by anodization method, showing high surface and strong chemical stability in acidic and basic media, have been employed for the application to the electrodes for water splitting in KOH solution. Due to its high polarization resistance of $TiO_2$ itself, proper catalysts are essentially required to reduce overpotentials for water oxidation and reduction. Most of academic literature showed noble metal catalysts for foreign dopants in $TiO_2$ electrodes. From commercialization point of view, screening of low-cost catalyst is important. Herein, we propose molybdenum oxide as low-cost catalysts among various catalysts tested in the experiments, which exhibits the highest performance for hydrogen evolution reaction in highly alkaline solution. We showed that molybdenum oxide doped electrode can be operated in extreme acidic and basic conditions as well.