Coverage-dependent activation of CO over Ni/Cu(100) single atom alloys (SAAs).

Single atom alloys (SAAs) often bring new chemistry in heterogeneous catalysis and well-defined structure for the study of structure-activity relationship (SAR). However, the existing pressure gap causes the reported SARs quite divergent. Herein, we have studied CO activation over Ni/Cu(100) SAAs in ultrahigh vacuum (UHV) and millibar range. While the Ni SAAs formed on Cu(100) significantly enhance the CO adsorption strength under UHV conditions, the CO treatment at elevated pressure leads to notable surface carbon and oxygen deposition through surface reaction. Density functional theory calculations revealed that either dissociation or disproportionation is thermodynamically forbidden for the coverage of CO less than 5/16 ML. However, these two reaction pathways can be opened at higher CO coverages due to the elevated energy state involving repulsion between adsorbed CO. This work uncovers the initial activation process of CO and demonstrates one typical cause for the pressure gap in surface science study as well.

Shallow donor states induced by in-diffused Cu in ZnO: a combined HREELS and hybrid DFT study.

A combined experimental and first principles study of Cu defects in bulk ZnO is presented. Cu particles are epitaxially deposited on the polar O-ZnO(0001) surface at room temperature. Upon heating, a broadening of the quasielastic peak in high resolution electron energy loss spectra is observed, corresponding to an electronic doping effect of Cu atoms in bulk ZnO with an ionization energy of 88 meV. Cu impurities in ZnO, although commonly acting as acceptors, are presently observed to induce shallow donor states. We assign these to interstitial Cu species on the basis of a hybrid density functional study.

Exploring the Interactions of Oxygen with Defective ZnO.

Exploring the interactions of oxygen with defective oxide is of importance to understand the microscopic process and performance of ZnO-based oxygen sensors. The interactions of environmental oxygen with vacuum-annealed defective ZnO have been studied by electrical methods, vacuum Fourier transform infrared spectroscopy, and in situ adsorption experiments. It was found that the vacuum-annealed defective ZnO exhibits varied electrical response at different temperatures, which, by vacuum IR investigation, was ascribed to the subtle balance between formation of oxygen vacancies and their interactions with environmental oxygen. Further studies showed that two microscopic steps including surface adsorption and bulk diffusion were dominating the interactions between defective ZnO and environmental oxygen, and the corresponding apparent activation energies were estimated to be 0.093 and 0.67 eV through in situ adsorption experiments. The quite low activation barrier of oxygen adsorption on the defective ZnO was proposed to be responsible for the extreme high sensitivity of ZnO-based oxygen sensors.

A Newly Designed Infrared Reflection Absorption Spectroscopy System for In Situ Characterization from Ultrahigh Vacuum to Ambient Pressure.

We present a novel ultrahigh vacuum (UHV) compatible polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) system that is designed for in situ surface spectroscopic characterization on a transferable single crystalline sample. The innovative design of manipulator rod and high-pressure cell (HPC) ensures free movement of the sample between the preparation chamber and the HPC, and perfect separation of them during high pressure experiments. The pressure in the HPC can be varied from UHV (10-9 mbar) to ambient pressure (1000 mbar) while keeping the preparation chamber under UHV conditions. The design of the transferable sample holder and receiving stage allows precise temperature measurement and allows convenient sample changing. In situ IRRAS measurements under variable pressure and temperature can be conducted either in the conventional mode or with polarization modulation. Other surface characterization methods can also use the preparation chamber; thus, the system is endowed with the capability for systematic investigations of surface catalytic reactions. A case study of CO adsorption and oxidation on Pt(111) demonstrates the performance of the system.

Ionization energies of shallow donor states in ZnO created by reversible formation and depletion of H interstitials.

The electronic effects of H atoms at interstitial sites in ZnO have been investigated by high resolution electron energy loss spectroscopy (HREELS). A reversible doping is achieved by exposing single crystalline (0001)-oriented ZnO substrates to atomic hydrogen. At low temperatures, interstitial H atoms form shallow donor states. At sufficiently high temperatures, the electrons are excited into the conduction band. We use EELS to demonstrate the presence of plasmons resulting from this finite density of charge carriers in the conduction band. Above temperatures of 100 K, a strong, plasmon-induced broadening of the quasielastic peak in the HREELS data is observed. The analysis of the temperature dependence yields a donor level ionization energy of 25+/-5 meV.

The identification of hydroxyl groups on ZnO nanoparticles by infrared spectroscopy.

The interaction of water with ZnO nanoparticles has been studied by means of diffuse reflectance infrared spectroscopy (DRIFTS) and ultra-high vacuum FTIR spectroscopy (UHV-FTIRS). Exposing clean ZnO powder to water at 323 K leads to both molecular and dissociative adsorption of H2O forming a number of hydroxyl species. All the OH bands are clearly identified by the adsorption of D2O showing the expected isotopic shifts. According to the vibrational and thermal stability data obtained from single crystal surfaces, the OH species observed on ZnO nanoparticles are identified as follows: (1) OH group (3620 cm(-1)) on the polar O-ZnO(0001[combining macron]) surface formed via dissociation of water on oxygen vacancy sites; (2) partial dissociation of water on the mixed-terminated ZnO(101[combining macron]0) surface yielding coexistent H2O ( approximately 3150 and 3687 cm(-1)) and OH species (3672 cm(-1)), where the molecularly adsorbed H2O is further identified by the characteristic scissoring mode at 1617 cm(-1); (3) isolated OH species (3639 and 3656 cm(-1)) formed on the mixed-terminated ZnO(101[combining macron]0) surface; (4) interaction of water with defects forming hydroxyl (or O-HO) species (3564 and 3448 cm(-1)).