Yuichiro Koike

A New XAFS Beamline NW10A at the Photon Factory

A new XAFS beamline NW10A using bending magnet radiation from 6.5 GeV PF‐AR has been constructed. NW10A consists of a Si(311) double crystal monochromator and a Pt‐coated bent cylindrical focusing mirror and provides focused X‐ray beam between 8 and 42 keV. The obtained flux through a 1mm square slit is 1×1010 ph/s at 20 keV and 7×109 ph/s at 30keV, which are 20 and 200 times more intense than obtained at BL‐10B. Platinum K‐edges do not degrade the quality of XAFS spectra when higher orders are properly reduced. High quality Ce K‐edge XAFS spectra are easily obtained.

Design of a high-temperature and high-pressure liquid flow cell for x-ray absorption fine structure measurements under catalytic reaction conditions

The design and performance of a new high-pressure and high-temperature cell for measurement of x-ray absorption fine structure (XAFS) spectra of solid catalysts working in a flowing liquid are presented. The cell has flat, high-purity sintered cubic boron nitride (c-BN) windows which can tolerate high temperature (900 K) and high pressure (10 MPa). The c-BN is a new material which has the highest tensile strength, second only to diamond, and is also chemically and thermally stable. The use of the cell is demonstrated for measurements of PtPdAl(2)O(3) and Ni(2)PSiO(2) hydrodesulfurization catalysts at reaction conditions. A technique called delta chi (Deltachi), involving determining the difference between XAFS spectra of the sample at reaction conditions and the bare sample, is introduced.

Local structure of Pt and Pd ions in Ce1−xTixO2: X-ray diffraction, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure

Ce(1-x-y)Ti(x)Pt(y)O(2-delta) (x=0.15; y=0.01) and Ce(1-x-y)Ti(x)Pd(y)O(2-delta) (x=0.25; y=0.02 and 0.05) are found to be good CO oxidation catalysts [T. Baidya et al., J. Phys. Chem. B 110, 5262 (2006); T. Baidya et al., J. Phys. Chem. C 111, 830 (2007)]. A detailed structural study of these compounds has been carried out by extended x-ray absorption fine structure along with x-ray diffraction and x-ray photoelectron spectroscopy. The gross cubic fluorite structure of CeO(2) is retained in the mixed oxides. Oxide ion sublattice around Ti as well as Pt and Pd ions is destabilized in the solid solution. Instead of ideal eight coordinations, Ti, Pd, and Pt ions have 4+3, 4+3, and 3+4 coordinations creating long and short bonds. The long Ti-O, Pd-O, and Pt-O bonds are approximately 2.47 A (2.63 A for Pt-O) which are much higher than average Ce-O bonds of 2.34 A.

Preparation and structure of a single Au atom on the TiO2(110) surface: control of the Au–metal oxide surface interaction

Three-dimensional Au structures on bare and organic-compound-modified TiO2(110) surfaces were interrogated by Au L3-edge polarization dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS) spectroscopy. On the bare TiO2(110) surface, icosahedral Au55 nanoclusters were the main product found. When the surfaces were modified with ortho or meso mercaptobenzoic acid (o-MBA or m-MBA), Au was atomically dispersed. Sulfur atoms in the o- and m- MBA formed strong covalent bonds with Au to produce stable Au-MBA (o- and m- forms) surface complexes. On the other hand, only oxygen atoms on the surface did not make a strong enough interaction to stabilize the Au species. We discuss how the Au species formed on the modified TiO2(110) surface and the possibility to control the Au structure by the surface modification method.

Improvement of the XANAM System and Acquisition of a Peak Signal with a High S/N ratio

We have made remarkable progress in detecting X-ray-induced frequency shift signals, which will promote development of a chemically sensitive NC-AFM. A highperformance controller provides a tenfold higher signal to noise ratio than that previously reported. We confirmed that the frequency shift or complementary Z-feedback signal dependence on X-ray energy has a peak. An important feature of the signal is that it does not follow the absorption spectrum of a surface element. These new findings are important to elucidate this novel X-ray-induced phenomenon.