• Journal of the Korean Ceramic Society
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• v.40 no.9
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• pp.842-848
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• 2003

Semiconducting $\alpha$-Fe$_2$O$_3$ film was prepared by the cathodic electrodeposition method on Indium Tin Oxide (ITO) substrate for photoelectrochemical cell application. After heat treatment at 50$0^{\circ}C$, the phase was changed from Fe to $\alpha$-Fe$_2$O$_3$. The phase, morphology, absorbance, and photocurrent density (A/$\textrm{cm}^2$) of the film depended on the preparation conditions: deposition time, applied voltage, and the duration of heat treatment. The $\alpha$-Fe$_2$O$_3$ film was characterized by X-Ray Diffractometer (XRD), Scanning Electron Microscope (SEM), and UV -Visible Spectrophotometer. The stability of the $\alpha$-Fe$_2$O$_3$ film in aqueous solution was tested at zero bias potential under the white-light source of 100 mW/$\textrm{cm}^2$. The apparent grain size of the films formed at -2.0 V was larger than that grown at -2.5 V. The $\alpha$-Fe$_2$O$_3$ film deposited at -2.0 V for 180 s and heat-treated at 50$0^{\circ}C$ for 1 h showed the predominant photocurrent of 834$\mu$A/$\textrm{cm}^2$.

• 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.

• Korean Journal of Materials Research
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• v.28 no.5
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• pp.261-267
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• 2018

Hydrothermal synthesis of highly crystalline $TiO_2$ nanorods is a well-developed technique and the nanorods have been widely used as the template for growth of various core-shell nanorod structures. Magneli/CdS core-shell nanorod structures are fabricated for the photoelectrochemical cell (PEC) electrode to achieve enhanced carrier transport along the metallic magneli phase nanorod template. However, the long and thin $TiO_2$ nanorods may form a high resistance path to the electrons transferred from the CdS layer. $TiO_2$ nanorods synthesized are reduced to magneli phases, $TixO_{2x-1}$, by heat treatment in a hydrogen environment. Two types of magneli phase nanorods of $Ti_4O_7$ and $Ti_3O_5$ are synthesized. Structural morphology and X-ray diffraction analyses are carried out. CdS nano-films are deposited on the magneli nanorods for the main light absorption layer to form a photoanode, and the PEC performance is measured under simulated sunlight irradiation and compared with the conventional $TiO_2/CdS$ core-shell nanorod electrode. A higher photocurrent is observed from the stand-alone $Ti_3O_5/CdS$ core-shell nanorod structure in which the nanorods are grown on both sides of the seed layer.

• Journal of Powder Materials
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• v.17 no.3
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• pp.216-222
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• 2010

Self-standing $TiO_2$ nanotube arrays were fabricated by potentiostatic anodic oxidation method using pure Ti foil as a working electrode and ethylene glycol solution as electrolytes with small addition of $NH_4F$ and $H_2O$. The influences of anodization temperature and time on the morphology and formation of $TiO_2$ nanotube arrays were investigated. The fabricated $TiO_2$ nanotube arrays were applied as a photoelectrode to dye-sensitized solar cells. Regardless of anodizing temperature and time, the average diameter and wall thickness of $TiO_2$ nanotube show a similar value, whereas the thickness show a different trend with reaction temperature. The thickness of $TiO_2$ nanotube arrays anodized at $20^{\circ}C$ and $30^{\circ}C$ was time-dependent, but on the other hand its at $10^{\circ}C$ are independent of anodization time. The conversion efficiency is low, which is due to a morphology breaking of the $TiO_2$ nanotube arrays in manufacturing process of photoelectrode.

• Korean Journal of Materials Research
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• v.29 no.1
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• pp.1-6
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• 2019

Recent industrialization has led to a high demand for the use of fossil fuels. Therefore, the need for producing hydrogen and its utilization is essential for a sustainable society. For an eco-friendly future technology, photoelectrochemical water splitting using solar energy has proven promising amongst many other candidates. With this technique, semiconductors can be used as photocatalysts to generate electrons by light absorption, resulting in the reduction of hydrogen ions. The photocatalysts must be chemically stable, economically inexpensive and be able to utilize a wide range of light. From this perspective, cuprous oxide($Cu_2O$) is a promising p-type semiconductor because of its appropriate band gap. However, a major hindrance to the use of $Cu_2O$ is its instability at the potential in which hydrogen ion is reduced. In this study, gold is used as a bottom electrode during electrodeposition to obtain a preferential growth along the (111) plane of $Cu_2O$ while imperfections of the $Cu_2O$ thin films are removed. This study investigates the photoelectrochemical properties of $Cu_2O$. However, severe photo-induced corrosion impedes the use of $Cu_2O$ as a photoelectrode. Two candidates, $TiO_2$ and $SnO_2$, are selected for the passivation layer on $Cu_2O$ by by considering the Pourbaix-diagram. $TiO_2$ and $SnO_2$ passivation layers are deposited by atomic layer deposition(ALD) and a sputtering process, respectively. The investigation of the photoelectrochemical properties confirmed that $SnO_2$ is a good passivation layer for $Cu_2O$.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.306-310
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• 2015

In this research, hematite nanoparticles were synthesized by DC thermal plasma process to increase the overall surface area. The effect of binders on hematite electrodes was investigated by changing the type and composition of binders when preparing electrodes. Nitrogen gas was also added to the DC thermal plasma process in order to dope the hematite with N for enhancing photoelectrochemical properties of hematite nanoparticles. The efficiency of water splitting reaction was measured by linear sweep voltammetry (LSV) under solar simulator. In LSV measurements, the onset potential and maximum current density at a fixed voltage were measured. The durability of electrodes was checked by repeating LSV measurements. CMC (carboxymethyl cellulose) binder with 50 : 1 composition exhibits the highest current density of $12mA/cm^2$ and CMC binder with 20 : 1 composition, showing the initial current density of $3mA/cm^2$, endures 20 times of repetitive LSV measurements. Effects of nitrogen doping on hematite nanoparticles were proven to be insignificant.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.87-87
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• 2010

Photoelectrochemical (PEC) systems are promising methods of producing H2 gas using solar energy in an aqueous solution. The photoelectrochemical properties of numerous metal oxides have been studied. Among them, the PEC systems based on TiO2 have been extensively studied. However, the drawback of a PEC system with TiO2 is that only ultraviolet (UV) light can be absorbed because of its large band gap (3.2 - 3.4 eV). Two approaches have been introduced in order to use PEC cells in the visible light region. The first method includes doping impurities, such as nitrogen, into TiO2, and this technique has been extensively studied in an attempt to narrow the band gap. In comparison, research on the second method, which includes visible light water splitting in molecular photosystems, has been slow. Mallouk et al. recently developed electrochemical water-splitting cells using the Ru(II) complex as the visible light photosensitizer. the dye-sensitized PEC cell consisted of a dye-sensitized TiO2 layer, a Pt counter electrode, and an aqueous solution between them. Under a visible light (< 3 eV) illumination, only the dye molecule absorbed the light and became excited because TiO2 had the wide band gap. The light absorption of the dye was followed by the transfer of an electron from the excited state (S*) of the dye to the conduction band (CB) of TiO2 and its subsequent transfer to the transparent conducting oxide (TCO). The electrons moved through the wire to the Pt, where the water reduction (or H2 evolution) occurred. The oxidized dye molecules caused the water oxidation because their HOMO level was below the H2O/O2 level. Organic dyes have been developed as metal-free alternatives to the Ru(II) complexes because of their tunable optical and electronic properties and low-cost manufacturing. Recently, organic dye molecules containing multi-branched, multi-anchoring groups have received a great deal of interest. In this work, tri-branched tri-anchoring organic dyes (Dye 2) were designed and applied to visible light water-splitting cells based on dye-sensitized TiO2 electrodes. Dye 2 had a molecular structure containing one donor (D) and three acceptor (A) groups, and each ended with an anchoring functionality. In comparison, mono-anchoring dyes (Dye 1) were also synthesized. The PEC response of the Dye 2-sensitized TiO2 film was much better than the Dye 1-sensitized or unsensitized TiO2 films.

• Membrane Journal
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• v.6 no.2
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• pp.101-108
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• 1996

The oxidation/degradation efficiency of formic acid through the photoelectrochemical reaction has been investigated as a basic research in order to develope the process for degrading toxic organic compounds dissolved in water. A $TiO_{2}$ photoelectro-membrane reactor for purification of water, in which filtration as well as photoelectrocatalytic oxidation of organic compounds could be carried out simultaneously, was developed. Porous $SnO_{2}$ tubes prepared by slip casting and commercial porous stainless steel tubes, being electrically conductive, were used as not only supports but also working electrodes. The UV light with the wavelength of 365 nm was applied as a light source for photocatalytic reactions. The photoelectrocatatytic composite membranes were prepared by coating the support surface with the $TiO_{2}$ sol of pH 1.45. The oxidation efficiency of formic acid increased with the reaction time and the applied voltage, but was almost independent of the solution flux. The results showed that more than 90% of formic acid could he dograded at 27V using the $TiO_{2}$/stainless steel composite membrane, while about 77% in case of the $TiO_{2}/SnO_{2}$ Composite membrane. It was also concluded that the oxidation efficiencies of formic acid could be significantly improved by about 6~7 times by the photoelectrochemical reaction in comparison with those by the photocatalytic reaction only.

• Korean Journal of Materials Research
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• v.26 no.11
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• pp.604-610
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• 2016

We report on the fabrication and characterization of a novel $Cu_2O/CuO$ heterojunction structure with CuO nanorods embedded in $Cu_2O$ thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a $Cu_2O$ thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/CuO$ heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/CuO$ photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. $-1.05mA/cm^2$ at -0.6 V vs. $Hg/HgCl_2$ in $1mM\;Na_2SO_4$ electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the $Cu_2O/CuO$ photocathode was estimated to be 1.27% at -0.6 V vs. $Hg/HgCl_2$. Moreover, the PEC current density versus time (J-T) profile measured at -0.5 V vs. $Hg/HgCl_2$ on the $Cu_2O/CuO$ photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple $Cu_2O$ thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.