Titanium dioxide (TiO 2 ) has a number of uses in catalysis, photochemistry, and sensing that are linked to the reducibility of the oxide. Usually, bridging oxygen (O br ) vacancies are assumed to cause the Ti 3d defect state in the band gap of rutile TiO 2 (110). From high-resolution scanning tunneling microscopy and photoelectron spectroscopy measurements, we propose that Ti interstitials in the near-surface region may be largely responsible for the defect state in the band gap. We argue that these donor-specific sites play a key role in and may dictate the ensuing surface chemistry, such as providing the electronic charge required for O 2 adsorption and dissociation. Specifically, we identified a second O 2 dissociation channel that occurs within the Ti troughs in addition to the O 2 dissociation channel in O br vacancies. Comprehensive density functional theory calculations support these experimental observations.

The direct reduction of CO 2 to CH 3 OH is known to occur at several types of electrocatalysts including oxidized Cu electrodes. In this work, we examine the yield behavior of an electrodeposited cuprous oxide thin film and explore relationships between surface chemistry and reaction behavior relative to air-oxidized and anodized Cu electrodes. CH 3 OH yields (43 lmol cm À2 h À1 ) and Faradaic efficiencies (38%) observed at cuprous oxide electrodes were remarkably higher than air-oxidized or anodized Cu electrodes suggesting Cu(I) species may play a critical role in selectivity to CH 3 OH. Experimental results also show CH 3 OH yields are dynamic and the copper oxides are reduced to metallic Cu in a simultaneous process. Yield behavior is discussed in comparison with photoelectrochemical and hydrogenation reactions where the improved stability of Cu(I) species may allow continuous CH 3 OH generation.

Large-amplitude electron density oscillations were observed on a Be(0001) surface by means of variable-temperature scanning tunneling microscopy. Fourier transforms of the images showed a ring of radius 2kF, where kF is the Fermi wave vector of the Be(0001) surface state. This wavelength was expected from Friedel oscillations caused by electronic screening of surface defects, but the amplitude of the waves for energies near the Fermi energy was anomalously large and inconsistent with the Friedel concept of screening. The enhanced amplitude of the waves must be a many-body effect, either in the electron gas (possibly an incipient charge density wave) or in the response of the lattice (electron-phonon coupling).