• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2133-2139
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• 2012

A new system using $TiO_2$ (nano-sized, band-gap 3.14 eV)-impregnated spherical ZnS (micro-sized, band-gap 2.73 eV) nano/micro-composites (Ti 0.001, 0.005, 0.01, and 0.05 mol %/ZnS) was developed to enhance the production of hydrogen from methanol/water splitting. The ZnS particles in a spherical morphology with a diameter of about 2-4 mm which can absorb around 455 nm were prepared by hydrothermal method. This material was used as a photocatalyst with loading by nano-sized $TiO_2$ (20-30 nm) for hydrogen production. The evolution of $H_2$ from methanol/water (1:1) photo splitting over the $TiO_2$/ZnS composite in the liquid system was enhanced, compared with that over pure $TiO_2$ and ZnS. In particular, 1.2 mmol of $H_2$ gas was produced after 12 h when 0.005 mol % $TiO_2$/ZnS nano/micro-composite was used. On the basis of cyclic voltammeter (CV) and UV-visible spectrums results, the high photoactivity was attributed to the larger band gap and the lower LUMO in the $TiO_2$/ZnS composite, due to the decreased recombination between the excited electrons and holes.

• 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.

• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2813-2817
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• 2014

A new magnetic semiconductor material was synthesized to enable separation after a liquid-type photocatalysis process. Core@shell-structured $CuFeS_2@TiO_2$ magnetic nanoparticles were prepared by a combination of solvothermal and wet-impregnation methods for photocatalysis applications. The materials obtained were characterized using X-ray diffraction, transmission electron microscopy, ultraviolet-visible, photoluminescence spectroscopy, Brunauer-Emmett-Teller surface area measurements, and cyclic voltammetry. This study confirmed that the light absorption of $CuFeS_2$ was shifted significantly to the visible wavelength compared to pure $TiO_2$. Moreover, the resulting hydrogen production from the photo-splitting methanol/water solution after 10 hours was more than 4 times on the core@shell structured $CuFeS_2@TiO_2$ nanocatalyst than on either pure $TiO_2$ or $CuFeS_2$.

• Clean Technology
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• v.18 no.4
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• pp.355-359
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• 2012

For effectively photochemical hydrogen production, Ti ions (0.01, 0.10, 0.50 mol%) impregnated $WO_3$ ($Ti/WO_3$) nanometer sized particles were prepared using a impregnation method as a photocatalyst. The characteristics of the synthesized $Ti/WO_3$ photocatalysts were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectra (PL), atomic force microscope (AFM), and electrostatic force microscope (EFM). The evolution of $H_2$ from methanol/water (1/1) photo-splitting over $Ti/WO_3$ photocatalysts was enhanced compared to those over pure $TiO_2$ and $WO_3$ photocatalysts; 3.02 mL of $H_2$ gas was evolved after 8 h when 0.5 g of a 0.10 mol% $Ti/WO_3$ catalyst was used.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.513-517
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• 2013

This study focused on the synthesis of $Nb_xSrTi_{1-x}O_3$ photocatalysts which partially inserted Nb ions with excellent ability of fluorescence into the perovskite structured $SrTiO_3$ frameworks and their photocatalytic hydrogen productions from methanol/water splitting corresponding to the molar ratios of Ti and Nb. The characteristics of the synthesized $SrTiO_3$ and $Nb_xSrTi_{1-x}O_3$ powders were analyzed by X-ray diffraction (XRD), energy dispersive X-ray spectrometer (EDS), and UV-Visible spectrometer. The hydrogen evolution from methanol/water photo-splitting was enhanced over $Nb_{0.05}SrTi_{0.95}O_3$ compared to those over $SrTiO_3$ and another $Nb_xSrTi_{1-x}O_3$; 4.9 mL of hydrogen gases was collected after 8 h when 0.5g of $Nb_{0.05}SrTi_{0.95}O_3$ catalyst was used in pH 10.

• Clean Technology
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• v.17 no.1
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• pp.78-82
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• 2011

For effectively photochemical hydrogen production, P (negative semiconductor) and B (positive semiconductor) ions (0.1, 0.2, 0.5, and 1.0 mol%) incorporated $TiO_2$ (P- and B-$TiO_2$) nanometer sized particles were prepared using a solvothermal method as a photocatalyst. The characteristics of the synthesized P- and B-$TiO_2$ photocatalysts were analyzed by X-ray Diffraction (XRD), Transmission electron microscopy (TEM), W-visible spectroscopy (UV-Vis), and Photoluminescence spectra (PL). The evolution of $H_2$ from methanol/water (1:1) photo-splitting over B-$TiO_2$ photocatalysts was enhanced compared to those over pure $TiO_2$ and P-$TiO_2$ photocatalysts; 0.42 mL of $H_2$ gas was evolved after 10 h when 0.5 g of a 1.0 mol% B-$TiO_2$ catalyst was used.

• 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.