• Journal of the Korean Chemical Society
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• v.42 no.6
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• pp.618-628
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• 1998

Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800$^{\circ}C$ to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction(XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally $p(CH_4)/p(O_2)=250$ Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best $C_2$ yield of 8.0% with a selectivity of 43.2% at 775$^{\circ}C$. The $C_2$ selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO([Mn] > 6.3 mol%) catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the $C_2$ selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000$^{\circ}C$ at Po2's of $10^{-3}\; to\;10^{-1}\;atm.$ The electrical conductivity was decreased with Mn-doping and increased with increasing $P0_2$in the range of $10^{-3}\;to\;10^{-1}\;atm,$ indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry.

• Journal of the Korean Vacuum Society
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• v.20 no.6
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• pp.395-402
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• 2011

The nanomechanical properties of fully lithiated and unlithiated silicon nanowire deposited on silicon substrate have been studied with atomic force microscopy. Silicon nanowires were synthesized using the vapor-liquid-solid process on stainless steel substrates using Au catalyst. Fully lithiated silicon nanowires were obtained by using the electrochemical method, followed by drop-casting on the silicon substrate. The roughness, derived from a line profile of the surface measured in contact mode atomic force microscopy, has a smaller value ($0.65{\pm}0.05$ nm) for lithiated silicon nanowire and a higher value ($1.72{\pm}0.16$ nm) for unlithiated silicon nanowire. Force spectroscopy was utilitzed to study the influence of lithiation on the tip-surface adhesion force. Lithiated silicon nanowire revealed a smaller value (~15 nN) than that of the Si nanowire substrate (~60 nN) by a factor of two, while the adhesion force of the silicon nanowire is similar to that of the silicon substrate. The elastic local spring constants obtained from the force-distance curve, also shows that the unlithiated silicon nanowire has a relatively smaller value (16.98 N/m) than lithiated silicon nanowire (66.30 N/m) due to the elastically soft amorphous structures. The frictional forces of lithiated and unlithiated silicon nanowire were obtained within the range of 0.5-4.0 Hz and 0.01-200 nN for velocity and load dependency, respectively. We explain the trend of adhesion and modulus in light of the materials properties of silicon and lithiated silicon. The results suggest a useful method for chemical identification of the lithiated region during the charging and discharging process.