NO dissociation on Cu(111) and Cu2O(111) surfaces: a density functional theory based study.

NO dissociation on Cu(111) and Cu(2)O(111) surfaces is investigated using spin-polarized density functional theory. This is to verify the possibility of using Cu-based catalyst for NO dissociation which is the rate limiting step for the NO(x) reduction process. The dissociation of molecularly adsorbed NO on the surface is activated for both cases. However, from the reaction path of the NO-Cu(2)O(111) system, the calculated transition state lies below the reference energy which indicates the possibility of dissociation. For the NO-Cu(111) system, the reaction path shows that NO desorption is more likely to occur. The geometric and electronic structure of the Cu(2)O(111) surface indicates that the surface Cu atoms stabilize themselves with reference to the O atom in the subsurface. The interaction results in modification of the electronic structure of the surface Cu atoms of Cu(2)O(111) which greatly affects the adsorption and dissociation of NO. This phenomenon further explains the obtained differences in the dissociation pathways of NO on the surfaces.

Anomalous metallic state in the vicinity of metal to valence-bond solid insulator transition in LiVS2.

We investigate LiVS2 and LiVSe2 with a triangular lattice as itinerant analogues of LiVO2 known for the formation of a valence-bond solid (VBS) state out of an S=1 frustrated magnet. LiVS2, which is located at the border between a metal and a correlated insulator, shows a first order transition from a paramagnetic metal to a VBS insulator at Tc approximately 305 K upon cooling. The presence of a VBS state in the close vicinity of insulator-metal transition may suggest the importance of itinerancy in the formation of a VBS state. We argue that the high temperature metallic phase of LiVS2 has a pseudogap, likely originating from the VBS fluctuation. LiVSe2 was found to be a paramagnetic metal down to 2 K.

Dual nature of a Ni dopant in the hole-type La2-xSrxCuO4 cuprate superconductor.

Local distortions around a Ni dopant in the hole-type La2-xSrxCuO4 superconductor system were studied by x-ray-absorption fine structure (XAFS) using single crystals over a wide hole-doping range. Two distinct interatomic distances between Ni and in-plane oxygen appear in the Ni K-edge extended XAFS. Combined with previous results on hole-localization effects by Ni doping, two types of charge states are strongly indicated for Ni. This duality disqualifies a magnetic-impurity picture for Ni dopant in the superconducting phase of cuprates.

Charge-ordered state in single-crystalline CaFeO3 thin film studied by x-ray anomalous diffraction.

X-ray anomalous diffraction, together with a band-structure calculation, was employed to obtain a quantitative understanding of the charge-ordering state in a single-crystalline CaFeO3 thin film. The experimental result shows a characteristic energy dispersion of the nearly inhibited reflection at 150 K, implying Fe atoms split into two distinct states. The energy dispersion is in good agreement with the calculated spectrum based on the LDA+U scheme. The calculation also reveals an electronic structure of the system where holes in the oxygen orbital surround one of the distinct Fe atoms, in spite of the total electron number in both Fe atoms remaining unchanged.

Self-regeneration of a Pd-perovskite catalyst for automotive emissions control.

Catalytic converters are widely used to reduce the amounts of nitrogen oxides, carbon monoxide and unburned hydrocarbons in automotive emissions. The catalysts are finely divided precious-metal particles dispersed on a solid support. During vehicle use, the converter is exposed to heat, which causes the metal particles to agglomerate and grow, and their overall surface area to decrease. As a result, catalyst activity deteriorates. The problem has been exacerbated in recent years by the trend to install catalytic converters closer to the engine, which ensures immediate activation of the catalyst on engine start-up, but also places demanding requirements on the catalyst's heat resistance. Conventional catalyst systems thus incorporate a sufficient excess of precious metal to guarantee continuous catalytic activity for vehicle use over 50,000 miles (80,000 km). Here we use X-ray diffraction and absorption to show that LaFe(0.57)Co(0.38)Pd(0.05)O(3), one of the perovskite-based catalysts investigated for catalytic converter applications since the early 1970s, retains its high metal dispersion owing to structural responses to the fluctuations in exhaust-gas composition that occur in state-of-the-art petrol engines. We find that as the catalyst is cycled between oxidative and reductive atmospheres typically encountered in exhaust gas, palladium (Pd) reversibly moves into and out of the perovskite lattice. This movement appears to suppress the growth of metallic Pd particles, and hence explains the retention of high catalyst activity during long-term use and ageing.

EXAFS spectra above Pb and Pt K edges observed at low temperature.

X-ray absorption spectra near K edges of Pb (88.0keV) and Pt (78.4keV) for the foils were measured in transmission mode at SPring-8. We succeeded for the first time in observing the EXAFS oscillation of the Pb foil at 12K, although it was failed at room temperature in a previous experiment. The amplitude of the EXAFS oscillation of the Pt foil at 12K considerably increased in comparison with that at room temperature, indicating that the amplitude is very sensitive to the Debye-Waller factor at high-k values.

Structural changes of quartz-type crystalline and vitreous GeO2 under pressure.

Using a large volume high pressure apparatus, quartz-type crystalline GeO2 and Li2O-4GeO2 glass have been compressed up to 14 GPa at room temperature and their local structural changes have been investigated by an in-situ XAFS method. In quartz-type crystalline GeO2, the change of the coordination number from 4 to 6 begins above 8 GPa and finishes below 12 GPa. On decompression, reversal transition begins below 8 GPa and there is a large hysteresis. Almost no sixfold coordination of Ge is preserved after releasing pressure. Change of coordination number in vitreous Li2O-4GeO2 begins above 6 GPa and is completed below 10 GPa. Reversal transition begins below 10 GPa and the hysteresis is smaller than that of quartz-type GeO2. Change of coordination number in vitreous Li2O-4GeO2 is also reversal.

XAFS in the high-energy region.

XAFS (X-ray absorption fine-structure) spectra were measured near K-absorption edges of Ce (40.5 keV), Dy (53.8 keV), Ta (67.4 keV) and Pt (78.4 keV). The blunt K-edge jump due to the finite lifetime of the core hole was observed. This makes it difficult to extract EXAFS (extended X-ray absorption fine-structure) functions at low k values. Local structure parameters can be evaluated from the EXAFS spectra above K-absorption edges in the high-energy region as well as from those above L(III)-edges. It was found that the finite-lifetime effect of the core hole is effectively taken into the photoelectron mean-free-path term, as predicted theoretically.