• Bulletin of the Korean Chemical Society
• /
• v.33 no.7
• /
• pp.2133-2139
• /
• 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
• /
• v.35 no.9
• /
• pp.2813-2817
• /
• 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 $CuFeS_2$.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.5
• /
• pp.1047-1053
• /
• 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 Chemical Engineering Research
• /
• v.51 no.4
• /
• pp.513-517
• /
• 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
• /
• v.18 no.4
• /
• pp.355-359
• /
• 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.

• Applied Chemistry for Engineering
• /
• v.27 no.6
• /
• pp.555-564
• /
• 2016

In recent years, methanol has attracted much attention since it can be cleanly manufactured by the combined use of atmospheric $CO_2$ recycling and water splitting via renewable energy. For the concept of "methanol economy", an active methanol synthesis catalyst should be prepared in a sophisticated manner rather than by empirical optimization approach. Even though Cu/ZnO-based catalysts prepared by coprecipitation are well known and have been extensively investigated even for a century, fundamental understanding on the precipitation chemistry and catalyst nanostructure has recently been achieved due to complexity of the necessary preparation steps such as precipitation, ageing, filtering, washing, drying, calcination and reduction. Herein we review the recent reports regarding the effects of various synthesis variables in each step on the physicochemical properties of materials in precursor, calcined and reduced states. The relationship between these characteristics and the catalytic performance will also be discussed because many variables in each step strongly influence the final catalytic activity, called "chemical memory". All discussion focuses on how to prepare a highly active Cu/ZnO-based catalyst for methanol synthesis. Furthermore, the preparation strategy we deliver here would be utilized for designing other coprecipitation-derived supported metal or metal oxide catalysts.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2010.05a
• /
• pp.3.1-3.1
• /
• 2010

Water splitting reaction using photocatalysts is of great interest in the utilization of solar energy [1]. In the present work, visible light-responsive $TiO_2$ thin films (Vis-$TiO_2$) were prepared by a radio frequency magnetron sputtering (RF-MS) deposition method and applied for the separate evolution of $H_2$ and $O_2$ from water as well as the photofuel cell. Special attentions will be focused on the effect of HF treatment of Vis-$TiO_2$ thin films on their photocatalytic activities. Vis-$TiO_2$ thin films were prepared by an RF-MS method using a calcined $TiO_2$ plate and Ar as the sputtering gas. The Vis-$TiO_2$ thin films were then deposited on the Ti foil substrate with the substrate temperature at 873 K (Vis-$TiO_2$/Ti). Vis-$TiO_2$/Ti thin films were immersed in a 0.045 vol% HF solution at room temperature. The effect of HF treatments on the activity of Vis-$TiO_2$/Ti thin films for the photocatalytic water splitting reaction have been investigated. Vis-$TiO_2$/Ti thin films treated with HF solution (HF-Vis-$TiO_2$/Ti) exhibited remarkable enhancement in the photocatalytic activity for $H_2$ evolution from a methanol aqueous solution as well as in the photoelectrochemical performance under visible light irradiation as compared with the untreated Vis-$TiO_2$/Ti thin films. Moreover, Pt-loaded HF-Vis-$TiO_2$/Ti thin films act as efficient and stable photocatalysts for the separate evolution of $H_2$ and $O_2$ from water under visible light irradiation in the presence of chemical bias. Thus, HF treatment was found to be an effective way to improve the photocatalytic activity of Vis-$TiO_2$/Ti thin films. Furthermore, unique separate type photofuel cell was fabricated using a Vis-$TiO_2$ thin film as an electrode, which can generate electrical power under solar light irradiation by using various kinds of biomass derivatives as fuel. It was found that the introduction of an iodine ($I^-/{I_3}^-$) redox solution at the cathode side enables the development of a highly efficient photofuel cell which can utilize a cost-efficient carbon electrode as an alternative to the Pt cathode.

• Proceedings of the Korean Institute of Surface Engineering Conference
• /
• 2016.11a
• /
• pp.59-75
• /
• 2016

Reduced or black $TiO_{2-x}$ materials with oxygen-deficiency have been achieved by creating oxygen vacancies and/or defects at the surface using different methods. Fascinatingly, they exhibited an extended absorption in VIS and IR instead of only UV light with bandgap decrease from 3.2 (anatase) to ~1 eV. However, despite the dramatic enhancement of optical absorption in black $TiO_{2-x}$ materials, they have failed to show expected visible light-assisted water splitting efficiency. This was ascribed to the high concentration of the surface defects and/or oxygen vacancies, considered as an electron donor to enhance donor density and improve the charge transportation in black $TiO_2$ can also act as charge recombination centers, which eventually decrease photocatalytic activity. Therefore, a black ot reducd $TiO_2$ material with optimized properties would be highly desired for visible light photocatalysis. In this report, a new controlled magnesiothermic reduction has been developed to synthesize reduced black $TiO_{2-x}$ in the presence $H_2/Ar$ for photocatalytic $H_2$ production from methanol-water system. The material possesses an optimum band gap and band position, oxygen vacancies, and surface defects and shows significantly improved optical absorption in the visible and infrared region. The synergistic effects enable the reduced $TiO_{2-x}$ material to show an excellent hydrogen production ability along with long-term stability under the full solar wavelength range of light and visible light, respectively, in the methanol-water system in the presence of Pt as a co-catalyst. These values are superior to those of previously reported black $TiO_2$ materials. On the basis of all the results, it can be realized that the outstanding activity and stability of the reduced of $TiO_{2-x}$ NPs suggest that a balanced combination of different factors like $Ti^{3+}$, surface defects, oxygen vacancy, and recombination center is achieved along with optimized bandgap and band position during the preparation employing magnesiothermic reduction in the presence of $H_2$. The controlled magnesiothermic reduction in the presence of $H_2$ is one of the best alternative ways to produce active and stable $TiO_2-based$ photocatalyst for $H_2$ production.

• Clean Technology
• /
• v.21 no.4
• /
• pp.271-277
• /
• 2015

A photocatalyst which mixed by the commercialized P25-TiO₂ and a synthesized Ag_xO was used in an appropriate weight ratio to effectively produce hydrogen gas in this study. The Ag_xOs were synthesized with the conventional sol-gel method, and tetramethylammonium hydroxides were added at the synthesis process in order to stabilize the solutions, and then the solutions were heat-treated at the temperatures of -5, 25, and 50 ℃, resulted to obtain the three types of silver oxides. Physicochemical properties of the synthesized Ag_xOs were identified through X-ray diffraction analysis (XRD), scanning emission microscopy (SEM), ultraviolet-visible spectroscopy, and X-ray photoelectron spectroscopy (XPS). In the photolysis results of water/methanol (weight ratio 1:1) solution, the mixture of P25-TiO₂/Ag_xO exhibited a significantly higher hydrogen gases evolution, compared to that of pure P25-TiO₂. Additionally, the addition of H₂O₂ as an supplement oxidant and in Ag_xO synthesized at 50 ℃ improved the hydrogen production efficiency. In particular, the emitted hydrogen gases reached to 13,000 μmol during 8 hours when a mixed catalyst, Ag_xO of 0.1 g and P25-TiO₂ of 0.9 g, were used.

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