• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.749-752
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• 2009

Anodized tubular titania ($TiO_2$) electrodes (ATTEs) are prepared and used as both the photoanode and the cathode substrate in a photoelectrochemical system designed to split water into hydrogen with the assistance of an enzyme and an external bias (solar cell). In particular, the ATTE used as the cathode substrate for the immobilization of the enzyme is prepared by two methods; adsorption and crosslinking. Results show that the optimized amount of enzyme is 10.98 units for the slurried enzyme, 3.66 units for the adsorbed one and 7.32 units for the crosslinked one, and the corresponding hydrogen evolution rates are 33.04, 148.58, and 234.88 umol/hr, respectively. The immobilized enzyme, specifically the chemically crosslinked one, seems to be much superior to the slurried enzyme, due to the enhanced charge-transfer process that is caused by the lower electrical resistance between the enzyme and the ATTE. This results in a greater number of accepted electrons and a larger amount of enzymes able to deal with the electrons.

• Journal of Hydrogen and New Energy
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• v.18 no.2
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• pp.151-156
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• 2007

Solar cell and nanofiltration membrane were utilized in a system of enzymatic hydrogen production through light-sensitized photoanode, which resembles photoelectrochemical(PEC) configuration. Solar cell uses no additional light energy to increase energy for electrons to reduce protons and for holes to oxidize water to oxygen, and nanofiltration membrane replaces a salt bridge successfully with increased ion transport capability. With this system configuration, optimized amount of enzyme(10.98 unit), and an anodized tubular $TiO_2$ electrode($5^{\circ}C$/1 hr in 0.5 wt% HF-$650^{\circ}C$/5 hr) hydrogen evolved at a rate of ca. $43\;{\mu}mol/(cm^2{\times}hr)$ in a cathodic compartment and oxygen generated at a rate of ca. $20\;{\mu}mol/(cm^2{\times}hr)$ in an anodic compartment. The stoichiometric evolution of gases indicated that water was splitted in the system.

• Journal of Hydrogen and New Energy
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• v.21 no.4
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• pp.301-306
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• 2010

The present work is performed to photocatalytically reduce Cr(VI) by means of metal deposited anodized $TiO_2$ tubes, which are prepared by anodization of Ti foil followed by metal deposition. Stably immobilized photo-reactive materials are favored in the field of detoxification in a conventional aqueous medium, preventing gradual loss of efficiency and process malfunction due to detachment of the materials. The prepared samples are characterized by SEM, TEM, EDAX, and photocurrent. The metal deposited-$TiO_2$ electrode shows higher efficiency for Cr(VI) reduction (ca. 20%) and higher ability for adsorption (4~5 times) than pure one.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.227.2-227.2
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• 2010

본 연구에서는 양극산화된 $TiO_2$ 전극(anodized tubular $TiO_2$ electrode, ATTE)을 수소제조용 PEC(Photoelectrochemical)시스템에서 광어노드와 기존의 백금전극을 대체하고 $H^+$ 환원능을 향상시키기 위하여 엔자임(Pyrococcus furiosus, Pfu)을 고정화한 후 캐소드로 동시에 활용하였으며, 엔자임 고정을 위한 crosslinker 종류 및 금속담지 여부, ATTE 길이를 통한 수소발생양에 미치는 영향을 연구하였다. ATTE 표면과 엔자임의 amine group의 연결을 위하여 heterobifunctional crosslinker로써 사슬 길이가 상대적으로 짧은 Sulfo-SDA가 유리하였으며, 금속담지의 경우 짧은 튜브의 경우 1% 내에서 효과가 증진되었으나 긴 튜브의 경우는 오히려 광전류 및 궁극적으로 수소발생속도에 불리하게 작용하였다. 또한, 튜브 길이가 긴 ATTE가 짧은 ATTE 보다 수소발생양에서 더욱 효율적임을 알 수 있었다. 텅스텐산화물 담지의 가시광감응에의 담지 효과는 예비 실험 결과로 나타나지 않아, 추가적인 연구가 필요한 것으로 판단된다.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.222-225
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• 2009

In this paper, $TiO_2$ nanotube is prepared and the preparation is influenced by electrochemical etching rate and chemical dissolution rate. Especially, the chemical dissolution rate is lowered as the length $TiO_2$ nanotube increases. Titanium foil were anodized at various bias or current such as 20V, 55V and 0.1A (bath temperature $25^{\circ}C$) in organic electrolytes (ethylene glycol, glycerol) and then annealed at $450^{\circ}C$ and $650^{\circ}C$ to obtain the crystallized tubular $TiO_2$ on the Ti foil. Higher efficiency (89.1%) for the Cr(VI) reduction was obtained with the prepared sample compared to that (20.9%) with the sample in 0.5% HF electrolyte earlier studied.

• Journal of Hydrogen and New Energy
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• v.18 no.4
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• pp.452-457
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• 2007

Titanium foil and mesh(anodized tubular $TiO_2$ electrode, ATTE) were anodized in a bath at $5^{\circ}C$ with 20V external bias applied, then annealed at different temperatures($450^{\circ}C{\sim}850^{\circ}C$) to obtain tubular $TiO_2$ on the Ti substrate. The prepared sample was used to investigate rate of hydrogen production as well as Cr(VI) reduction. The ATTEs annealed at relatively lower temperatures showed higher activity than those at relatively higher temperatures. In particular, the Cr(VI) reduction was pH-dependent. To improve photocatalytic Cr(VI) reduction with the ATTEs, two configurations, fixing foil type and rotating mesh type, were also compared. As a result, the rotating mesh type was much more effective for Cr(VI) reaction than the former due to the more efficient use of the light. In the rotating type reactor, as the rotating speed increased, the rate of the Cr(VI) reduction was getting faster.

• Journal of Sensor Science and Technology
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• v.27 no.4
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• pp.264-268
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• 2018

Vertically-aligned $TiO_2$ nanotube electrodes have attracted considerable attention for applications in solar cells, catalysts, and sensors, because of their ideal structure for electron transport and electrolyte diffusion. Here, we prepare vertically-aligned $TiO_2$ nanotube electrodes using a two-step anodization process. The prepared $TiO_2$ nanotube electrodes exhibit uniform pore structures with an inner diameter of ~80-90 nm and wall thickness of ~20-25 nm. In addition, they exhibit an anatase crystal phase after a high-temperature annealing. The annealed $TiO_2$ nanotube electrodes are applied in dye-sensitized solar cells (DSSCs) as photoanodes. The fabricated DSSC exhibits conversion efficiencies of 3.46 and 2.15% with liquid- and gel-type electrolytes, respectively.

• Journal of Hydrogen and New Energy
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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.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.100-100
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• 2011

Nanomaterial architecture with highly ordered, vertically oriented $TiO_2$ nanotube arrays shows a good promise for diverse technological applications. As inspired from the literature reports that Nickel modification can improve the photocatalytic activity of $TiO_2$, it was planned to coat Ni into the $TiO_2$ matrix. In this study, first $TiO_2$ nanotubes(TiNTs) were prepared by anodization (60V,3min) in HF-free aqueous electrolyte on ultrasonically cleaned polished titanium sheet substrates ($1{\times}7cm^2$). The typical thickness of the sintered TiNT ($500^{\circ}C$for10min) was ~1 micronas confirmed from the FESEM study. In the next part, as-anodized and sintered TiNT/Ti photoanodes were used to coat Ni by AC electrodeposition from aqueous 0.1M nickel sulphate solution. During AC electrodeposition, conditions such as 1V DC offset voltage, 9V amplitude (peak-to-peak) and 750 Hz frequency were fixed constant and the deposition time was varied as 0.5 min, 1 min, 2 min and 10 min. The photoelectrochemical performance of pristine and Ni modified TiNT/Ti photoanodes was measured in 1N NaOH electrolyte under 1 SUN illumination in the potential range of -1V and 1.2V versus Ag/AgCl reference electrode. The photocurrent performance of TiNT/Ti photoanode decreased upon Ni modification and the results were confirmed after repeated experiments. This suggests us that Ni modification inhibits the photoelectrochemical performance of $TiO_2$ nanotubes.

• Journal of Hydrogen and New Energy
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• v.22 no.4
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• pp.432-442
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• 2011

Anodized tubular $TiO_2$ electrodes (ATTEs) with three noticeably different lengths are prepared to determine their optimum length for the photo-driven activity in the reaction of Cr(VI) reduction and hydrogen evolution. The ATTEs with ethylene glycol have longer $TiO_2$ tubes (7-15.6 ${\mu}m$) than those with hydrfluoric acid (0.6-0.8 ${\mu}m$). These samples, which differ only in the length of the tubes, with a wall thickness of ca. 20 nm, consist mainly of an anatase crystalline phase after heat treatment at $650^{\circ}C$, since the anatase crystallites at the tube walls do not undergo transformation into rutile phase, due to the constraints imposed by the wall thickness. Among them, the medium size (ca. 8 ${\mu}m$) tubes provide the optimum conditions, irrespective of the light intensity, which is explained in terms of the correlation between the amount of photons and the adsorbed electron acceptors and their location. Photocatalytic Cr(VI) reduction leads to ca. 60% reduction of Cr(VI) even under 1 sun irradiation with the medium-sized anodized $TiO_2$ tubes, but only ca. 20% with the short- and long-sized tubes. For hydrogen evolution, tubes longer than 8 ${\mu}m$ do not exhibit better performance with any light intensity.