• Journal of the Korean institute of surface engineering
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• v.55 no.4
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• pp.215-221
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• 2022

In the present work, copper oxide thin films were formed by heat-treatment method with different temperatures and atmosphere, e.g., at 200 ~ 400 ℃; in air and Ar atmosphere. The morphological, electrical and optical properties of the thermally fabricated Cu oxide films were analyzed by SEM, XRD, and UV-VIS spectrometer. Thereafter, photoelectrochemical properties of the thermal copper oxide films were analyzed under solar light (AM 1.5, 100 mW/cm²). Conclusively, the highest photocurrent was obtained with Cu₂O formed under the optimum annealing condition at 300 ℃ in air atmosphere. In addition, EIS results of Cu oxide formed in air atmosphere showed relatively low resistance and long electron life-time compared with Cu Oxide fabricated in Ar atmosphere at the same temperature. This is because heat-treatment in Ar atmosphere could not form Cu₂O due to lack of oxygen, and thermally formed CuO at high temperature suppressed stability and conductivity of the Cu oxide.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.3
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• pp.244-249
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• 2007

The present work considers the concept of enzymatic photoelectrochemical generation of hydrogen through water splitting using a Xe lamp as a source of light. A solar cell was applied to the system in order to shift the level of electrochemical energy of the system, resulting in the rate of hydrogen production at $43\;{\mu}mol/(cm^2{\times}hr)$ in cathodic compartment with an anodized tubular $TiO_2$ electrode(ATTE, $5^{\circ}C$/1hr in 0.5 wt% HF-$650^{\circ}C$/5hr). The trend of the rate of hydrogen production, for the ATTEs with different annealing temperature from $350^{\circ}C$ to $850^{\circ}C$, fairly well coincided with the photoelectrical properties measured by potentiostat. The actual chemical bias through imposition of two electrolytes of different pHs between anode(13.68) and cathode(7.5) was 0.24eV.

• 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.

• Journal of Electrochemical Science and Technology
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• v.2 no.4
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• pp.187-192
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• 2011

Photoelectrochemical performances of ZnO electrodes are enhanced by coupling with cobalt-based catalyst (CoPi) in phosphate electrolyte (pH 7). For this study, hexagonal pillar-shaped ZnO nanorods are grown on ZnO electrodes through a chemical bath deposition, onto which CoPi is deposited with different photodeposition times (10-30 min). A scanning electron microscopic study indicates that CoPi deposition does not induce any change of ZnO morphology and an energy-dispersive X-ray spectroscopic analysis shows that inorganic phosphate ions (Pi) exist on ZnO surface. Bare ZnO electrodes generate the current of ca. $0.36mA/cm^2$ at a bias potential of 0.5 V vs. SCE, whereas ZnO/CoPi (deposited for 10 min) has ca. 50%-enhanced current ($0.54mW/cm^2$) under irradiation of AM 1.5G-light ($400mW/cm^2$). The excess loading of CoPi on ZnO results in decrease of photocurrents as compared to bare ZnO likely due to limited electrolyte access to ZnO and/or CoPi-mediated recombination of photogenerated charge carriers. The primary role of CoPi is speculated to trap the photogenerated holes and thereby oxidize water into molecular oxygen via an intervalency cycle among Co(II), Co(III), and Co(IV).

• Journal of the Korea Institute of Military Science and Technology
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• v.20 no.4
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• pp.491-496
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• 2017

The hydrogen($H_2$) is promising energy carrier of renewable energy in the microgrid system such as small village and military base due to its high energy density, pure emission and convenient transportation. $H_2$ can be generated by photocatalytic water splitting, gasification of biomass and water electrolysis driven by solar cell or wind turbine. Solid oxide electrolysis cells(SOECs) are the most efficient way to mass production due to high operating temperature improving the electrode kinetics and reducing the electrolyte resistance. The SOECs are consist of nickel-yttria stabilized zirconia(NiO-YSZ) fuel electrode / YSZ electrolyte / lanthanum strontium manganite-YSZ(LSM-YSZ) air electrode due to similarity to Solid Oxide Fuel Cells(SOFCs). The Ni-YSZ most widely used fuel electrode shows several problems at SOEC mode such as degradation of the fuel electrode because of Ni particle's redox reaction and agglomeration. Therefore Ni-YSZ need to be replaced to an alternative fuel electrode material. In this study, We studied on the Double perovskite $PrBrMnO_{5+{\delta}}$(PBMO) due to its high electric conductivity, catalytic activity and electrochemical stability. PBMO was impregnated into the scaffold electrolyte $La_{0.8}Sr_{0.2}Ga_{0.85}Mg_{0.15}O_{3-{\delta}}$(LSGM) to be synthesized at low temperature for avoiding secondary phase generated when it exposed to high temperature. The Half cell test was conducted at SOECs and SOFCs modes.

• Journal of Electrochemical Science and Technology
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• v.14 no.4
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• pp.388-396
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• 2023

Photoelectrochemical (PEC) water splitting is a vital source of clean and sustainable hydrogen energy. Moreover, the large-scale H₂ production is currently necessary, while long-term stability and high PEC activity still remain important issues. In this study, a GaN-based photoelectrode was modified by an additional NH₃ treatment (900℃ for 10 min) and its PEC behavior was monitored. The bare GaN exhibited a highly crystalline wurtzite structure with the (002) plane and the optical bandgap was approximately 3.2 eV. In comparison, the NH₃-treated GaN film exhibited slightly reduced crystallinity and a small improvement in light absorption, resulting from the lattice stress or cracks induced by the excessive N supply. The minor surface nanotexturing created more surface area, providing electroactive reacting sites. From the surface XPS analysis, the formation of an N-Ga-O phase on the surface region of the GaN film was confirmed, which suppressed the charge recombination process and the positive shift of E_FB. Therefore, these effects boosted the PEC activity of the NH₃-treated GaN film, with J values of approximately 0.35 and 0.78 mA·cm^-2 at 0.0 and 1.23 V_RHE, respectively, and an onset potential (V_on) of -0.24 V_RHE. In addition, there was an approximate 50% improvement in the J value within the highly applied potential region with a positive shift of V_on. This result could be explained by the increased nanotexturing on the surface structure, the newly formed defect/trap states correlated to the positive V_on shift, and the formation of a GaO_xN_1-x phase, which partially blocked the charge recombination reaction.

• Journal of the Microelectronics and Packaging Society
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• v.23 no.4
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• pp.113-117
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• 2016

Recently, hydrogen is regarded as important energy in the future, because it is clean and renewable. The photoelectrochemical (PEC) system, which produce hydrogen using water splitting by solar energy, is one of the most promising energy systems because it has abundant energy sources and good theoretical efficiency. GaN has recently been regarded as suitable photoelectrode that could be used to split water to generate hydrogen without extra bias because its band edge position include water redox potential ($V_{redox}=1.23$ vs. SHE). GaN also shows considerable corrosion resistance in aqueous solutions and it is possible to control its properties, such as structure, band gap, and catalyst characteristics, in order to improve solar energy conversion efficiency. But, even if the band edge position of GaN make PEC reaction facilitate without bias, the overpotential of oxygen evolution reaction could reduce the efficiency of system. One of the ways to decrease overpotential is introduction of co-catalyst on photoelectrode. In this paper, we will investigate the effect of manganese dioxide ($MnO_2$) as a co-catalyst. $MnO_2$ particles were dispersed on GaN photoelectrode by spincoater and analyzed properties of the PEC system using potentiostat (PARSTAT4000). After coating $MnO_2$, the flat-band potential ($V_{fb}$) and the onset voltage ($V_{onset}$) were moved negatively by 0.195 V and 0.116 V, respectively. The photocurrent density increased on $MnO_2$ coated sample and time dependence was also improved. These results showed $MnO_2$ has an effect as a co-catalyst and it would enhance the efficiency of overall PEC system.

• Bulletin of the Korean Chemical Society
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• v.28 no.11
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• pp.2089-2092
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• 2007

Tantalum-containing metal oxides, well known for their efficiency in water splitting and H2 production, have never been used in visible light driven photodecomposition of H2S and H2 production. The present work is an attempt in this direction and investigates their efficiency. A mixed metal oxide, ZnFe2Ta2O9, with the inclusion of Fe2O3 to impart color, was prepared by the conventional ceramic route in single- and double-calcinations (represented as ZnFe2Ta2O9-SC and ZnFe2Ta2O9-DC respectively). The XRD characterization shows that both have identical patterns and reveals tetragonal structure to a major extent and a minor contribution of orthorhombic crystalline system. The UV-visible diffuse reflection spectra demonstrate the intense, coherent and wide absorption of visible light by both the catalysts, with absorption edge at 650 nm, giving rise to a band gap of 1.9 eV. Between the two catalysts, however, ZnFe2Ta2O9-DC has greater absorption in almost the entire wavelength region, which accounts for its strong brown coloration than ZnFe2Ta2O9-SC when viewed by the naked eye. In photocatalysis, both catalysts decompose H2S under visible light irradiation (λ ≥ 420 nm) and produce solar H2 at a much higher rate than previously reported catalysts. Nevertheless, ZnFe2Ta2O9-DC distinguishes itself from ZnFe2Ta2O9-SC by exhibiting a higher efficiency because of its greater light absorption. Altogether, the tantalum-containing mixed metal oxide proves its efficient catalytic role in H2S decomposition and H2 production process also.

• Journal of Electrochemical Science and Technology
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• v.9 no.4
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• pp.282-291
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• 2018

The pristine fluorine-doped $SnO_2$ (abbreviated as FTO) inverse opal (IO) was developed using a 410 nm polystyrene bead template. The nanolayered copper tungsten oxide ($CuWO_4$) was decorated on the FTO IO film using a facile electrochemical deposition, subsequently followed by annealing at $500^{\circ}C$ for 90 min. The morphologies, crystalline structure, optical properties and photoelectrochemical characteristics of the FTO and $CuWO_4$-decorated FTO (briefly denoted as $FTO/CuWO_4$) IO film were investigated by field emission scanning electron microscopy, X-ray diffraction, UV-vis spectroscopy and electrochemical impedance spectroscopy, showing FTO IO in the hexagonally closed-pack arrangement with a pore diameter and wall thickness of about 300 nm and 20 nm, respectively. Above this film, the $CuWO_4$ was electrodeposited by controlling the cycling number in cyclic voltammetry, suggesting that the $CuWO_4$ formed during 4 cycles (abbreviated as $CuWO_4$(4 cycles)) on FTO IO film exhibited partial distribution of $CuWO_4$ nanoparticles. Additional distribution of $CuWO_4$ nanoparticles was observed in the case of $FTO/CuWO_4$(8 cycles) IO film. The $CuWO_4$ layer exhibits triclinic structure with an indirect band gap of approximately 2.5 eV and shows the enhanced visible light absorption. The photoelectrochemical (PEC) behavior was evaluated in the 0.5 M $Na_2SO_4$ solution under solar illumination, suggesting that the $FTO/CuWO_4$(4 cycles) IO films exhibit a photocurrent density ($J_{sc}$) of $0.42mA/cm^2$ at 1.23 V vs. reversible hydrogen electrode (RHE, denoted as $V_{RHE}$), while the FTO IO and $FTO/CuWO_4$(8 cycles) IO films exhibited a $J_{sc}$ of 0.14 and $0.24mA/cm^2$ at $1.23V_{RHE}$, respectively. This difference can be explained by the increased visible light absorption by the $CuWO_4$ layer and the favorable charge separation/transfer event in the cascading band alignment between FTO and $CuWO_4$ layer, enhancing the overall PEC performance.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1137-1144
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• 2013

$TiO_2$ composites with seven different carbon materials (activated carbons, graphite, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene oxides, and reduced graphene oxides) that are virgin or treated with nitric acid are prepared through an evaporation method. The photocatalytic activities of the as-prepared samples are evaluated in terms of $H_2$ production from aqueous methanol solution (photo-catalytic reduction: PCR) and degradation of aqueous pollutants (phenol, methylene blue, and rhodamine B) (photocatalytic oxidation: PCO) under AM 1.5-light irradiation. Despite varying effects depending on the kinds of carbon materials and their surface treatment, composites typically show enhanced PCR activity with maximum 50 times higher $H_2$ production as compared to bare $TiO_2$. Conversely, the carbon-induced synergy effects on PCO activities are insignificant for all three substrates. Colorimetric quantification of hydroxyl radicals supports the absence of carbon effects. However, platinum deposition on the binary composites displays the enhanced effect on both PCR and PCO reactions. These differing effects of carbon materials on PCR and PCO reactions of $TiO_2$ are discussed in terms of physicochemical properties of carbon materials, coupling states of $TiO_2$/carbon composites, interfacial charge transfers. Various surface characterizations of composites (UV-Vis diffuse reflectance, SEM, FTIR, surface area, electrical conductivity, and photoluminescence) are performed to gain insight on their photocatalytic redox behaviors.