• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2442-2444
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• 2007

CO adsorbates on the surface of Pt supported on carbon catalysts (Pt/C) were investigated by CO stripping voltammetry. Three types of CO adsorbed samples were prepared: by methanol dehydrogenation only (COm), by CO gas bubbling only (COg), and by methanol dehydrogenation followed by CO gas bubbling (COm+g). Our coverage data show that CO gas can be adsorbed on Pt/C catalyst already saturated with CO adsorbates by methanol dehydrogenation. The COm+g sample showed the properties of both COm as well as COg samples in terms of the potential although the CO adsorbed by dehydrogenation was completely exchanged with CO in the electrolyte solution. Therefore, the oxidation pathways of CO on Pt/C were observed to depend on the initial adsorption conditions of CO more strongly than on the CO coverage. Our results imply that an initial CO poisoning condition in fuel cell operation is an important factor to determine the difficulty in removing the adsorbed CO and confirm that the properties of the adsorbed CO do not change even with chemical replacement with CO in different conditions. In addition, our results indicate a low CO surface mobility on the Pt in an electrolyte solution.

• Bulletin of the Korean Chemical Society
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• v.23 no.8
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• pp.1135-1138
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• 2002

CuO/ZnO, CuO/SiO,sub>2, and CuO/ZrO2 catalysts were prepared for investigating the support effects on methanol dehydrogenation. It was found that the conversion of methanol was proportional to the copper surface area on Cu/ZnO cat alysts and was independent on that on Cu/ZrO2 and Cu/SiO2. The highest copper surface area was obtained with the Cu/ZrO2 (9/1). The unusual deactivation of the Cu/ZnO, which showed the highest selectivity among the catalysts tested, was observed. Pulse reaction with methanol indicated that the lattice oxygen in ZnO could be removed by forming CO2 in the catalytic reaction, supporting that the ZnO reduction was responsible for the severe deactivation of the Cu/ZnO.

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.698-706
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• 1996

Dehydrogenation of methanol to produce formaldehyde was carried out over various silica-alumina catalysts doped with alkali metals in a continuous flow system. The reaction was rather dependent on Lewis acid than Br${\ddot{o}}$nsted acid suggesting that dehydrogenation of methanol was an electronic reaction. The Br${\ddot{o}}$nsted acid sites on silica-alumina were neutralized by doping with alkali metals, and the neutralization effect of Br${\ddot{o}}$nsted acid was dependent on the electron-donating capacity of the dopant metals. Activation energy for dehydrogenation of methanol decreased when Br${\ddot{o}}$nsted acid was neutralized by doping with K.

• Journal of Photoscience
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• v.2 no.1
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• pp.7-11
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• 1995

Powders of artificial crystallites of titanium(IV) oxide, TiO$_2$(B), were synthesized by the calcination of tetratitanic acid (hydrate, $H_2Ti_4O_9H_2O$; TTA). The relating titanates, potassium octatitanate ($K_2Ti_8O_{17}$) and octatitanic acid($H_2Ti_8O_{17}$), were also prepared. These powders, loaded with small amount of Pt, were suspended in an aqueous solution of 2-propanol and irradiated under argon atmosphere at 298 K + 0.5 deg. All the photocatalysts tested in this study produced almost equimolar amount of acetone and molecular hydrogen (H$_2$). Among them TiO$_2$(B) and TYA showed the higher photocatalytic activity but rather lower than commercial titanium(IV) oxide (TiO$_2$) powders. The photocatalytic activity of TiO$_2$(B) for 2-propanol dehydrogenation in deaerated aqueous suspension increased with the elevating calcination temperature. Comparison of rate of H$_2$ formation from methanol and 2-propanol solutions by the TiO$_2$(B) photocatalyst suggested a possibility of selection of substrate with its molecular size by TiO$_2$(B)

• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.197-204
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• 2003

The intracluster ion-molecule reactions of $Ti^+(H_2O)_n,\;Ti^+(CH_3OCH_3)_n,\;and\;Ti^+(CH_3OD)_n$ complexes produced by the mixing of the laser-vaporized plasma and the pulsed supersonic beam were studied using a reflectron time-of-flight mass spectrometer. The reactions of $Ti^+$ with water clusters were dominated by the dehydrogenation reaction, which produces $TiO^+(H_2O)_n$ clusters. The mass spectra resulting from the reactions of $Ti^+\;with\;CH_3OCH_3$ clusters exhibit a major sequence of $Ti^+(OCH_3)_m(CH_3OCH_3)_n$ cluster ions, which is attributed to the insertion of $Ti^+$ ion into C-O bond of $CH_3OCH_3$ followed by $CH_3$ elimination. The prevalence of $Ti^+(OCH_3)_m(CH_3OD)_n$ ions in the reaction of $Ti^+\;with\;CH_3OD$ clusters suggests that D elimination via O-D bond insertion is the preferred decomposition pathway. In addition, the results indicate that consecutive insertion reactions by the $Ti^+$ ion occur for up to three precursor molecules. Thus, examination of $Ti^+$ insertion into three different molecules establishes the reactivity order: O-H > C-O > C-H. The experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.