Adsorption and reaction of methanol over CeO(X)(100) thin films.

Methanol was adsorbed on oxidized and reduced CeOX(100) thin films to probe the active sites and reaction selectivity of these surfaces compared to those of CeOX(111). Roughly twice as much methoxy was formed on oxidized CeO2(100) compared to that formed on CeO2(111). In addition to more methoxy, hydroxyl is also more stable on CeO2(100). Unlike on CeO2(111), however, methanol on CeO2(100) produced CO, CO2, and H2 in addition to water and formaldehyde. The behavior of CeO2(100) is related to its surface structure, which provides greater access to Ce cations and therefore more active adsorption sites and more highly undercoordinated Ce and O. The undercoordinated O may explain the enhanced dehydrogenation activity leading to CO and H2 formation. The reduction of ceria leads to increased methanol uptake on both CeO2 - X(100) and CeO2 - X(111). However, although the uptake doubled on reduced CeO2 - X(111) compared to the oxidized surface, it increased by only 10% on reduced CeO2 - X(100) compared to that on fully oxidized CeO2(100). Reduction of both surfaces leads to a greater production of CO and H2. Reaction on all surfaces progresses rapidly from methoxy to products. There is no spectroscopic evidence of formyl or formate intermediates. On CeOX(100), carbonate is detected that decomposes into CO2 at high temperature.

Lateral manipulation of single-walled carbon nanotubes on H-passivated Si(100) surfaces with an ultrahigh-vacuum scanning tunneling microscope.

Ultrahigh-vacuum (UHV) scanning tunneling microscopy (STM) can be used for the manipulation of individual atoms and molecules into complex arrangements for sensitive electrical and structural characterization. However, the systematic UHV STM manipulation of single-walled carbon nanotubes (SWNTs), high-aspect-ratio molecular wires derived from graphene that exist in both semiconducting and metallic forms, has yet to be reported. In this work, we demonstrate the room-temperature lateral manipulation of approximately 1-nm-diameter SWNTs on UHV-prepared, hydrogen-passivated Si(100) surfaces. We show the reproducible actuation of SWNTs having lengths as small as 13 nm, along with the partial division of a two-tube bundle. Moreover, UHV STM desorption of H at the SWNT/Si interface is introduced as a means of locally strengthening the interaction between the tube and the surface. The UHV STM manipulation scheme described here is potentially extensible to the orientational control of SWNTs interfaced with atomically clean semiconducting surfaces, such as InAs(110), GaAs(110), and unpassivated Si(100), for which first-principles calculations based on density functional theory have been reported recently in the literature.