Role of residual transition-metal atoms in oxygen reduction reaction in cobalt phthalocyanine-based carbon cathode catalysts for polymer electrolyte fuel cell

Kobayashi, Masaki*; Niwa, Hideharu*; Harada, Yoshihisa*; Horiba, Koji*; Oshima, Masaharu*; Ofuchi, Hironori*; Terakura, Kiyoyuki*; Ikeda, Takashi; Koshigoe, Yuka*; Ozaki, Junichi*; et al.

Journal of Power Sources, 196(20), p.8346 - 8351, 2011/10

https://doi.org/10.1016/j.jpowsour.2011.06.062

The electronic structure of Co atoms in CoPc-based carbon catalysts, which were prepared by pyrolyzing a mixture of CoPc and phenol resin polymer up to 1000C, has been investigated using XAFS analysis and HXPES. The Co K XAFS spectra show that most of the Co atoms are in the metallic state and small quantities of oxidized Co components are present in the samples even after acid washing to remove Co atoms. Based on the difference in probing depth between XAFS and HXPES, it was found that after acid washing, the surface region with the aggregated Co clusters is primarily composed of metallic Co. Since the electrochemical properties remain almost unchanged even after the acid washing process, the residual metallic and oxidized Co atoms themselves will hardly contribute to the ORR activity of the CoPc-based carbon cathode catalysts, implying that the active sites of the CoPc-based catalysts primarily consist of light elements such as C and N.

X-ray photoemission spectroscopy analysis of N-containing carbon-based cathode catalysts for polymer electrolyte fuel cells

Niwa, Hideharu*; Kobayashi, Masaki*; Horiba, Koji*; Harada, Yoshihisa*; Oshima, Masaharu*; Terakura, Kiyoyuki*; Ikeda, Takashi; Koshigoe, Yuka*; Ozaki, Junichi*; Miyata, Seizo*; et al.

Journal of Power Sources, 196(3), p.1006 - 1011, 2011/02

https://doi.org/10.1016/j.jpowsour.2010.08.054

We report on the electronic structure of three different types of N-containing carbon-based cathode catalysts for polymer electrolyte fuel cells observed by hard X-ray photoemission spectroscopy. C 1s spectra show the importance of carbon network formation for the oxygen reduction reaction (ORR) activity. Samples having high oxygen reduction reaction activity in terms of oxygen reduction potential contain high concentration of graphite-like nitrogen. Based on a quantitative analysis of our results, the oxygen reduction reaction activity of the carbon-based cathode catalysts will be improved by increasing concentration of graphite-like nitrogen in a developed carbon network.

Spectroscopic characterization of ultrashort laser driven targets incorporating both Boltzmann and particle-in-cell models

Sherrill, M. E.*; Abdallah, J.*; Csanak, G.*; Dodd, E. S.*; Fukuda, Yuji; Akahane, Yutaka; Aoyama, Makoto; Inoue, Norihiro*; Ueda, Hideki*; Yamakawa, Koichi; et al.

High-Power Laser Ablation VII (Proceedings of SPIE Vol.7005), p.70051R_1 - 70051R_11, 2008/06

Coupled electron and atomic kinetics through the solution of the Boltzmann equation for generating time-dependent X-ray spectra

Sherrill, M. E.*; Abdallah, J. Jr.*; Csanak, G.*; Kilcrease, D. P.*; Dodd, E. S.*; Fukuda, Yuji; Akahane, Yutaka; Aoyama, Makoto; Inoue, Norihiro*; Ueda, Hideki; et al.

Journal of Quantitative Spectroscopy & Radiative Transfer, 99(1-3), p.584 - 594, 2006/05

https://doi.org/10.1016/j.jqsrt.2005.05.047

In this work, we present a model that solves self-consistently the electron and atomic kinetics to characterize highly non-equilibrium plasmas, in particular for those systems where both the electron distribution function is far from Maxwellian and the evolution of the ion level populations are dominated by time dependent atomic kinetics. In this model, level populations are obtained from a detailed collisional-radiative model where collision rates are computed from a time varying electron distribution function obtained from the solution of the zero-dimensional Boltzmann equation. The Boltzmann collision term includes the effects of electron-electron collisions, electron collisional ionization, excitation and de-excitation. An application for He spectra from a short pulse laser irradiated argon cluster target will be shown to illustrate the results of our model.

Measurement of ' X-ray transitions from 1 m Kr clusters irradiated by high-intensity femtosecond laser pulses

Hansen, S. B.*; Fournier, K. B.*; Faenov, A. Y.*; Magunov, A. I.*; Pikuz, T. A.*; Skobelev, I. Y.*; Fukuda, Yuji; Akahane, Yutaka; Aoyama, Makoto; Inoue, Norihiro*; et al.

Physical Review E, 71(1), p.016408_1 - 016408_9, 2005/01

https://doi.org/10.1103/PhysRevE.71.016408

X-ray line emission from ' transitions in Ne-like Kr and nearby ions has been observed from 1 m Kr clusters irradiated by fs-scale laser pulses at the JAERI facility in Kyoto, Japan. The dependence of X-ray spectral features and intensity on the incident laser intensity is rather weak, indicating that the 1-2 ps cluster lifetimes limit the number of ions beyond Ne-like Kr that can be produced by collisional ionization. A collisional-radiative model based on the relativistic multiconfigured FAC code has been constructed and used to determine that the cluster plasma has electron densities near 10 cm, temperature of a few hundred eV and hot electron fraction of a few percent.

Relativistic laser plasma from micron-sized argon clusters as a debris-free X-ray source for pulse X-ray diffraction

Fukuda, Yuji; Akahane, Yutaka; Aoyama, Makoto; Inoue, Norihiro*; Ueda, Hideki; Nakai, Yoshiki*; Tsuji, Koichi*; Yamakawa, Koichi; Hironaka, Yoichiro*; Kishimura, Hiroaki*; et al.

Applied Physics Letters, 85(21), p.5099 - 5101, 2004/11

https://doi.org/10.1063/1.1823589

We have demonstrated diffraction from Si(111) crystal using X-rays from highly ionized Ar ions produced by laser irradiation with an intensity of 610 W/cm and a pulse duration of 30 fs acting upon micron-sized Ar clusters. The measured total photon flux and line width in the He line (3.14 keV) were 410 photons/shot/4sr and 3.7 eV (FWHM), respectively, which is sufficient to utilize as a debris-free light source for time-resolved X-ray diffraction studies.

Evaluation in an Effect of Microorganism on Performance Assessment by COLFRAC

Kurosawa, Susumi; Sasaki, Ryoichi; Ueta, Shinzo*; Yoshikawa, Hideki

JNC TN8400 2004-012, 68 Pages, 2004/07

JNC-TN8400-2004-012.pdf:5.37MB

In order to evaluate the impact of microorganism by COLFRAC, which simulates colloid-facilitated contaminant migration, the microorganism - radionuclide sorption data and microbial films data in deep geological environment were surveyed. After the survey, the data conversion to be able to calculate the effect of them on performance assessment in COLFRAC has been undertaken. As the results of calculation by COLFRAC, the transport behavior of radionuclide may be enhanced, when radionuclide will be taken in the microorganism. Furthermore, the results indicated that the transport rate of radionuclide depends on microbial concentration.

Microdroplet evolution induced by a laser pulse

Smirnov, M. B.*; Skobelev, I. Y.*; Magunov, A. I.*; Faenov, A. Y.*; Pikuz, T. A.*; Fukuda, Yuji; Yamakawa, Koichi; Akahane, Yutaka; Aoyama, Makoto; Inoue, Norihiro*; et al.

Journal of Experimental and Theoretical Physics, 98(6), p.1123 - 1132, 2004/06

Interaction between high-power ultrashort laser pulse and giant clusters (microdroplets) consisting of 10 to 10 atoms is considered. The microdroplet size is comparable to the laser wavelength. A model of the evolution of a microdroplet plasma induced by a high-power laser pulse is developed, and the processes taking place after interaction with the pulse are analyzed. It is shown theoretically that the plasma is superheated: its temperature is approximately equal to the ionization potential of an ion having a typical charge. The microdroplet plasma parameters are independent of the pulse shape and duration. The theoretical conclusions are supported by experimental studies of X-ray spectra conducted at JAERI, where a 100-terawatt Ti-sapphire lasersystem was used to irradiate krypton and xenon microdroplets by laser pulses with pulse widths of 30 to 500 fs and intensities of 610 to 210 W/cm.

Many-electron dynamics of a Xe atom in strong and superstrong laser fields

Yamakawa, Koichi; Akahane, Yutaka; Fukuda, Yuji; Aoyama, Makoto; Inoue, Norihiro*; Ueda, Hideki; Utsumi, Takayuki*

Physical Review Letters, 92(12), p.123001_1 - 123001_4, 2004/03

https://doi.org/10.1103/PhysRevLett.92.123001

We report on detailed investigations of ionization dynamics of a Xe atom exposed to intense 800-nm pulses of 20-fs duration in the extensive intensity range from 10 to 10 W/cm. Ion yields of Xe to Xe were observed as a function of laser intensity and compared with the results from a single active electron based Ammosov-Delone-Krainov model. Unexpected ionization probabilities for lower charge states and also no interplay between the inner- and outer-shells by screening are inferred. Suppression of nonsequential ionization towards higher intensity and few optical cycle regimes is also proved.

X-ray radiation of clusters irradiated by ultrafast, high-intensity laser pulses

Fukuda, Yuji; Akahane, Yutaka; Aoyama, Makoto; Inoue, Norihiro*; Ueda, Hideki; Kishimoto, Yasuaki; Yamakawa, Koichi; Faenov, A. Y.*; Magunov, A. I.*; Pikuz, T. A.*; et al.

Laser-Generated & Other Lab. X-Ray & EUV Sources (Proceedings of SPIE Vol.5196), p.234 - 243, 2004/00

High resolution X-ray emission spectra of plasma created by laser irradiation of rare-gas (Ar, Kr, Xe) clusters have been measured at laser intensities over 10 W/cm and 30-fs pulse duration. To make these measurements possible, in addition to the effort to decrease a prepulse intensity using Pockels cell switches, micron-size clusters were produced using a specially designed conical nozzle. The Boltzmann equation and a detailed collisional radiative model are solved simultaneously as a function of time to model the time integrated X-ray spectra of the transient plasma. The results are quantitatively in good agreement with the experimentally observed X-ray emission spectra of Ar clusters.