Yohei Uemura

In situ time-resolved XAFS study on the structural transformation and phase separation of Pt3Sn and PtSn alloy nanoparticles on carbon in the oxidation process

The dynamic behavior and kinetics of the structural transformation of supported bimetallic nanoparticle catalysts with synergistic functions in the oxidation process are fundamental issues to understand their unique catalytic properties as well as to regulate the catalytic capability of alloy nanoparticles. The phase separation and structural transformation of Pt(3)Sn/C and PtSn/C catalysts during the oxidation process were characterized by in situ time-resolved energy-dispersive XAFS (DXAFS) and quick XAFS (QXAFS) techniques, which are element-selective spectroscopies, at the Pt L(III)-edge and the Sn K-edge. The time-resolved XAFS techniques provided the kinetics of the change in structures and oxidation states of the bimetallic nanoparticles on carbon surfaces. The kinetic parameters and mechanisms for the oxidation of the Pt(3)Sn/C and PtSn/C catalysts were determined by time-resolved XAFS techniques. The oxidation of Pt to PtO in Pt(3)Sn/C proceeded via two successive processes, while the oxidation of Sn to SnO(2) in Pt(3)Sn/C proceeded as a one step process. The rate constant for the fast Pt oxidation, which was completed in 3 s at 573 K, was the same as that for the Sn oxidation, and the following slow Pt oxidation rate was one fifth of that for the first Pt oxidation process. The rate constant and activation energy for the Sn oxidation in PtSn/C were similar to those for the Sn oxidation in Pt(3)Sn/C. In the PtSn/C, however, it was hard for Pt oxidation to PtO to proceed at 573 K, where Pt oxidation was strongly affected by the quantity of Sn in the alloy nanoparticles due to swift segregation of SnO(2) nanoparticles/layers on the Pt nanoparticles. The mechanisms for the phase separation and structure transformation in the Pt(3)Sn/C and PtSn/C catalysts are also discussed on the basis of the structural kinetics of the catalysts themselves determined by the in situ time-resolved DXAFS and QXAFS.

In situ time-resolved DXAFS for the determination of kinetics of structural changes of H-ZSM-5-supported active Re-cluster catalyst in the direct phenol synthesis from benzene and O2

Dynamic structural changes and their kinetics of a Re(10)-cluster catalyst in the direct phenol synthesis from benzene and O(2) were investigated by in situ time-resolved Re L(III)-edge energy-dispersive XAFS (DXAFS). We have successfully monitored the structural transformation of active Re(10) clusters to inactive Re monomers in the course of the selective oxidation of benzene with O(2) on the catalyst by the DXAFS technique in a real time. The results obtained suggested that the Re(10) cluster transformed directly to the Re monomers, which showed first order kinetics with respect to the quantity of Re(10) clusters. The absence of undesirable intermediate structures with low phenol selectivity during the structural transformation may be an advantageous issue for the high phenol selectivity of 93.9% at 9.9% conversion in a pulse reaction and 87.7% at 5.8% conversion in a steady-state reaction on the Re(10)-cluster catalyst. The reactant benzene inhibited the unfavorable structural transformation of the Re(10) cluster to the Re monomers during the selective benzene oxidation to phenol.

Performance and characterization of a Pt–Sn(oxidized)/C cathode catalyst with a SnO2-decorated Pt3Sn nanostructure for oxygen reduction reaction in a polymer electrolyte fuel cell

We have prepared and characterized a SnO2-decorated Pt-Sn(oxidized)/C cathode catalyst in a polymer electrolyte fuel cell (PEFC). Oxygen reduction reaction (ORR) performance of Pt/C (TEC10E50E) remained almost unchanged or even tended to reduce in repeated I-V load cycles, whereas the I-V load performance of the Pt-Sn(oxidized)/C prepared by controlled oxidation of a Pt-Sn alloy/C sample with the Pt3Sn phase revealed a significant increase with increasing I-V load cycles. The unique increase in the ORR performance of the Pt-Sn(oxidized)/C catalyst was ascribed to a promoting effect of SnO2 nano-islands formed on the surface of Pt3Sn core nanoparticles. Also in a rotating disk electrode (RDE) setup, the mass activity of an oxidized Pt3Sn/C catalyst was initially much lower than that of a Pt/C catalyst, but it increased remarkably after 5000 rectangular durability cycles and became higher than that of the fresh Pt/C. The maximum power density per electrochemical surface area for the Pt-Sn(oxidized)/C catalyst in a PEFC was about 5 times higher than that for the Pt/C catalyst at 0.1-0.8 A cm(-2) of the current density. In situ X-ray absorption near-edge structure (XANES) analysis at the Pt LIII-edge in increasing/decreasing potential operations and at the Sn K-edge in the I-V load cycles revealed a remarkable suppression of Pt oxidation compared with the Pt/C catalyst at higher potentials and no change in the Sn oxidation state, respectively, resulting in higher performance and stability of the Pt-Sn(oxidized)/C catalyst due to the SnO2 nano-islands under the PEFC operation conditions. The SnO2 nano-island decorated Pt-Sn(oxidized)/C catalyst with a Pt3Sn alloy nanostructure is regarded as a promising candidate for a PEFC cathode catalyst.

In situ study of an oxidation reaction on a Pt/C electrode by ambient pressure hard X-ray photoelectron spectroscopy

We have constructed an ambient pressure X-ray photoelectron spectroscopy instrument that uses hard X-ray radiation at the high-performance undulator beamline BL36XU of SPring-8. The dependence of the Au 4f peak intensity from Au foil on the ambient N2 pressure was measured. At a photon energy of 7.94 keV, the Au 4f peak intensity maintained 40% at 3000 Pa compared with that at high vacuum. We designed a polymer electrolyte fuel cell that allows us to perform X-ray photoelectron spectroscopy measurements of an electrode under working conditions. The oxidized Pt peaks were observed in the Pt 3d5/2 level of Pt nanoparticles in the cathode, and the peaks clearly depended on the applied voltage between the anode and cathode. Our apparatus can be applied as a valuable in situ tool for the investigation of the electronic states and adsorbed species of polymer electrolyte fuel cell electrode catalysts under the reaction conditions.

Non-secular part of nuclear dipolar broadening detected by zero-field spin relaxation of positive muon

Abstract The zero-field spin relaxation function of μ+ observed in ZrH2 has revealed that the second moment of the nuclear dipolar broadening is five times larger than the high-field value. This experiment clearly demonstrates the recovery of the non-secular part of dipolar interaction between unlike spins. A general expression of zero-field relaxation function is presented to account for a slow modulation of random fields on μ+ found at room temperature.

Dynamics of Photoelectrons and Structural Changes of Tungsten Trioxide Observed by Femtosecond Transient XAFS

The dynamics of the local electronic and geometric structures of WO3 following photoexcitation were studied by femtosecond time-resolved X-ray absorption fine structure (XAFS) spectroscopy using an X-ray free electron laser (XFEL). We found that the electronic state was the first to change followed by the local structure, which was affected within 200 ps of photoexcitation.

Deprotonation of a dinuclear copper complex of 3,5-diamino-1,2,4-triazole for high oxygen reduction activity

A dinuclear copper(II) complex of 3,5-diamino-1,2,4-triazole is one of the highly active copper-based catalysts for the oxygen reduction reaction (ORR) in basic solutions. Our in situ X-ray absorption near edge structure measurements revealed that deprotonation of the triazole ligand might cause coordination geometrical changes, resulting in the enhancement of the ORR activity.

Positive muon spin precession in magnetic oxides MnO and V2O3; local fields and phase transition

Muon spin precession is observed in the ordered state of antiferromagnetic oxides MnO and V2O3. An anomalous temperature dependence of muon precession frequency and the absence of critical behavior atTN are found in MnO and a hysterisis of the transition temperature is observed in V2O3. These results are explained in terras of the crystal distortion of these materials belowTN.

Paramagnetic shift of μ+ in MnO and its time dependence

ConclusionThe paramagnetic shift K of μ+ in MnO is measured from 140K to 420K. K is negative at 14OK, increases rapidly with increasing temperature, but does not show a linear relation to the susceptibility χ. At T = 170K and 230K, the value of K depends greatly on the fitting time-range of the spectrum. These features are explained by a “site change” of μ+ caused by its diffusion and trapping in the crystal.

Theory of the spin depolarisation rate of μ+ SR in pure Fe

Abstract The diffusion constant (D) and the spin depolarisation rate (λS) of the positive muon in the ferromagnetic b.c.c. lattices such as Fe have been calculated on the basis of the small polaron (SP) model with particular attention to the hopping and the coherent motions. They have been obtained in the forms: D= d 2 w D 6 and λ S = 4γ 2 μ H 2 d 3w S , where d is a jump length, and Hd is a magnitude of internal dipolar field. At high temperatures, the activated-type hopping motion gives a dominant contribution to wD, and wS coincides with wD. With decreasing temperature, wD turns to be increasing owing to the coherent motion. Whereas wS deviates from wD, after passing the minimum, to have a maximum, and then decreases in inverse proportion to a lifetime (B) of the SP band states. Because of the cell periodicity of the internal fields, the spin in an SP band state feels a definite magnetic field corresponding to the state, and sees various fields if scattered to other states. These scattering processes succeeding in a time shorter than (γμHd)-1 result in the motional narrowing of the spectra, with λS ⋍ γ2μHdB.