• Journal of Electrochemical Science and Technology
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• v.13 no.4
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• pp.504-504
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• 2022

• Journal of Hydrogen and New Energy
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• v.17 no.1
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• pp.21-30
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• 2006

[ $M/Fe_2O_3$ ] (M=Rh, Ce and Zr) mixed oxides were prepared using urea method to develop a medium for chemical hydrogen storage by their redox cycles. And their redox behaviors by repeated cycles were studied using temperature programmed reaction(TPR) technique. Additives such as Rh, Ce and Zr were added to iron oxides in order to lower the reaction temperature for reduction by hydrogen and re-oxidation by water-splitting. From the results, concentration of urea used as a precipitant had little effect on particle size and reduction property of iron oxide. TPR patterns of iron oxide consisted of two reduction peaks due to the course of $Fe_2O_3\;{\rightarrow}\;Fe_3O_4\;{\rightarrow}\;Fe$. The results of repeated redox tests showed that Rh added to iron oxide have an effect on lowering the re-oxidation temperature by water-splitting. Meanwhile, Ce and Zr additives played an important role in prevention of deactivation by repeated cycles. Finally, Fe-oxide(Rh, Ce, Zr) sample added with Rh, Ce and Zr showed the lowest re-oxidation temperature by water-splitting and maintained high $H_2$ recovery in spite of the repeated redox cycles. Consequently, it is expected that Fe-oxide(Rh, Ce, Zr) sample can be a feasible medium for chemical hydrogen storage using redox cycle of iron oxide.

• Korean Journal of Materials Research
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• v.28 no.4
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• pp.214-220
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• 2018

We report on the fabrication and photoelectrochemical(PEC) properties of a $Cu_2O$ thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in $Cu_2O$ thin film as an efficient photoelectrode for solar-driven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/ZnO$ p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/ZnO$ photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., $0.77mA/cm^2$ at 0.5 V vs $Hg/HgCl_2$ in a $1mM\;Na_2SO_4$ electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs $Hg/HgCl_2$, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

• 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 Hydrogen and New Energy
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• v.15 no.3
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• pp.201-207
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• 2004

Redox characteristics of metal oxide for hydrogen production by thermochemical water-splitting were investigated. $CuFe_2O_4$ as a redox pair that had a different molar ratio of Cu and Fe were prepared by co-precipitation method. Hydrogen production consisted of water-splitting step and thermal reduction step was performed below 1200K. Redox characteristics of Cu-ferrites were studied using the thermal gravimetric analysis technique. Also, structure change of Cu-ferrite during thermal reduction was investigated using the high temperature controlled XRD. In results, oxygen release of Cu-ferrite during the thermal reduction was initiated at oxygen site combined with Cu. Consequently, oxygen release amount of Cu-ferrite was increased with increase of Cu molar ratio of Cu-ferrite. It was found that thermal reduction of Cu-ferrite was begun at $875^\circ{C}$. It was confirmed that structure of Cu-ferrite was changed to metal and cation excess metal oxide during the thermal reduction step.

• Membrane Journal
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• v.13 no.1
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• pp.54-63
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• 2003

The Preparation and electrochemical characterization of anion-exchange membranes containing pyridinium groups were performed. As a result, the pyridinium membranes showed good electrochemical properties, comparable to those of the commercial membranes, with electrical resistance of less than $3.0 {\Xi}cm^2$ in a 0.5 mol $dm^{-3}$ NaCl and high ionic permselectivity (the transport number of $Cl^-$ ions being 0.97). Moreover, water splitting in the membranes containing pyridinium group was about two or three order of magnitude lower than those in the commercial membranes (ｅ.ｇ. AM-1, Tokuyama Crop., Japan) at the same current density because the resonance effedt in the quaternary aromatic pyridinium group contributed to their molecular stability. In addition, the electrodialytic properties of the pyridinium membranes were evaluated in a semi-pilot scale.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1047-1053
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• 2009

The future use of hydrogen as an energy source is expected to increase on account of its environmentally friendliness. In order to enhance the production of hydrogen, Pd ions (0.01, 0.05, 0.1, and 0.5 mol%) were incorporated $TiO_2$ (Pd-$TiO_2$) and used as a photocatalyst. The UV-visible absorbance decreased with increasing level of palladium incorporation without a wavelength shift. Although all the absorption plots showed excitation characteristics, there was an asymmetric tail observed towards a higher wavelength caused by scattering. However, the intensity of the photoluminescence (PL) curves of Pd-$TiO_2$ was smaller, with the smallest case being observed at 0.1 and 0.5 mol% Pd-$TiO_2$, which was attributedto recombination between the excited electrons and holes. Based on these optical characteristics, the evolution of $H_2$ from methanol/water (1:1) photo-splitting over Pd-$TiO_2$ in the liquid system was enhanced, compared with that over pure $TiO_2$. In particular, 2.4 mL of $H_2$ gas was produced after 8 h when 0.5 g of a 1.0 mol% Pd-$TiO_2$ catalyst was used. $H_2$ was stably evolved even after 28 h without catalytic deactivation, and the amount of $H_2$ produced reached 14.5 mL after 28 h. This is in contrast to the case of the Pd 0.1 mol% impregnated $TiO_2$ of $H_2$ evolution of 17.5 mL due to the more decreasedelectron-hole recombination.

• Korean Journal of Materials Research
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• v.29 no.3
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• pp.196-203
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• 2019

We report on the fabrication and characterization of an oxide photoanode with a zinc oxide (ZnO) nanorod array embedded in cuprous oxide ($Cu_2O$) thin film, namely a $ZnO/Cu_2O$ oxide p-n heterostructure photoanode, for enhanced efficiency of visible light driven photoelectrochemical (PEC) water splitting. A vertically oriented n-type ZnO nanorod array is first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film is directly electrodeposited onto the vertically oriented ZnO nanorod array to form an oxide p-n heterostructure. The introduction of $Cu_2O$ layer produces a noticeable enhancement in the visible light absorption. From the observed PEC current density versus voltage (J-V) behavior under visible light illumination, the photoconversion efficiency of this $ZnO/Cu_2O$ p-n heterostructure photoanode is found to reach 0.39 %, which is seven times that of a pristine ZnO nanorod photoanode. In particular, a significant PEC performance is observed even at an applied bias of 0 V vs $Hg/Hg_2Cl_2$, which makes the device self-powered. The observed improvement in the PEC performance is attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential including the light absorption and separation processes of photoinduced charge carriers, which provides a new avenue for preparing efficient photoanodes for PEC water splitting.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.29 no.4
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• pp.143-148
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• 2019

We have successfully fabricated high aspect-ratio GaN-based nanowires on Si substrates using molecular beam epitaxy (MBE) system for high-efficiency hydrogen generation of photoelectrochemical water splitting. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) demonstrated that p-GaN:Mg and p-InGaN nanowires were grown vertically on the substrate with high density. Furthermore, it was also confirmed that the emission wavelength of p-InGaN nanowire can be adjusted from 552 nm to 590 nm. Such high-aspect ratio p-InGaN nanowire structure will be a solid foundation for the realization of ultrahigh-efficiency photoelectrochemical water splitting through sunlight.

• Korean Journal of Materials Research
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• v.32 no.2
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• pp.98-106
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• 2022

Metal-organic frameworks (MOFs) are widely used in various fields because they make it easy to control porous structures according to combinations of metal ions and organic linkers. In addition, ZIF (zeolitic imidazolate framework), a type of MOF, is made up of transition metal ions such as Co²⁺ or Zn²⁺ and linkers such as imidazole or imidazole derivatives. ZIF-67, composed of Co²⁺ and 2-methyl imidazole, exhibits both chemical stability and catalytic activity. Recently, due to increasing need for energy technology and carbon-neutral policies, catalysis applications have attracted tremendous research attention. Moreover, demand is increasing for material development in the electrocatalytic water splitting and metal-air battery fields; there is also a need for bifunctional catalysts capable of both oxidation/reduction reactions. This review summarizes recent progress of bifunctional catalysts for electrocatalytic water splitting and metal-air batteries using ZIF-67. In particular, the field is classified into areas of thermal decomposition, introduction of heterogeneous elements, and complex formation with carbon-based materials or polyacrylonitrile. This review also focuses on synthetic methods and performance evaluation.