Surface-mediated visible-light photo-oxidation on pure TiO(2)(001).

We used STM to observe visible light photo-oxidation reactions of formic acid on the ordered lattice-work structure of a TiO(2)(001) surface for the first time. The nanostructured surface makes the band gap significantly smaller than 3.0 eV only at the surface layer, and the surface state of the crystal enables a visible light response.

Strong lateral electron coupling of pb nanowires on stepped si(111): angle-resolved photoemission studies.

We employ angle-resolved photoemission to characterize the electronic band structure of the Pb "nanowire" array self-assembled on a stepped Si(111) surface. Despite the highly oriented nanowires observed in scanning tunneling microscopy images, we find essentially two-dimensional Fermi contours modulated one dimensionally perpendicular to the wires. This strong two-dimensional and quasi-one-dimensional nature of the band structure explains the stability and anisotropy of the metallic phase down to 4 K as reported recently. A simple tight-binding model with each Si nanoterrace covered by a densely packed Pb overlayer successfully reproduces this modulated band structure and quantifies the electron coupling within the "nanostripes" and the step-edge potential.

Oxygen vacancy promoting catalytic dehydration of formic acid on TiO2(110) by in situ scanning tunneling microscopic observation.

The catalytic dehydration reaction processes of formic acid on a TiO2(110) surface at 350 K have been studied to visualize reaction intermediates and their dynamic behaviors by scanning tunneling microscopy. Three types of configurations of adsorbed formates on the surface were identified by their shapes and positions in STM images. Successive STM observations revealed transformations among the three configurations, i.e., bridge formate on a 5-fold coordinated Ti4+ row, bridge formate on an oxygen vacancy site with an oxygen atom of formate and on a 5-fold coordinated Ti4+ ion and with the other formate oxygen atom, and a monodentate formate on an oxygen vacancy site with an oxygen atom of formate. The decomposition of the monodentate formate to carbon monoxide and hydroxyl was also imaged, which is a rate-determining step in the catalytic dehydration of formic acid. Combined with first-principle DFT calculations, the overall reaction processes of the catalytic dehydration of formic acid on the surface have been elucidated. Oxygen vacancies on the surface that can be produced by dehydration of two hydroxyls in situ under the catalytic reaction conditions are essential for the reaction.

Electrical resistance of a monatomic step on a crystal surface.

We have succeeded in measuring the resistance across a single atomic step through a monatomic-layer metal on a crystal surface, Si(111)(sqrt[3]xsqrt[3])-Ag, using three independent methods, which yielded consistent values of the resistance. Two of the methods were direct measurements with monolithic microscopic four-point probes and four-tip scanning tunneling microscope probes. The third method was the analysis of electron standing waves near step edges, combined with the Landauer formula for 2D conductors. The conductivity across a monatomic step was determined to be about 5 x 10(3) Omega(-1) m(-1). Electron transport across an atomic step is modeled as a tunneling process through an energy-barrier height approximately equal to the work function.