Wetting induced oxidation of Pt-based nano catalysts revealed by high energy resolution X-ray absorption spectroscopy

Cui, Y.-T.*; Harada, Yoshihisa*; Niwa, Hideharu*; Hatanaka, Tatsuya*; Nakamura, Naoki*; Ando, Masaki*; Yoshida, Toshihiko*; Ishii, Kenji*; Matsumura, Daiju; Oji, Hiroshi*; et al.

Scientific Reports (Internet), 7(1), p.1482_1 - 1482_8, 2017/05

https://doi.org/10.1038/s41598-017-00639-1

Thickness-dependent magnetic properties and strain-induced orbital magnetic moment in SrRuO thin films

Ishigami, Keisuke*; Yoshimatsu, Kohei*; Toyota, Daisuke*; Takizawa, Masaru*; Yoshida, Teppei*; Shibata, Goro*; Harano, Takayuki*; Takahashi, Yukio*; Kadono, Toshiharu*; Verma, V. K.*; et al.

Physical Review B, 92(6), p.064402_1 - 064402_5, 2015/08

https://doi.org/10.1103/PhysRevB.92.064402

Thickness-dependent ferromagnetic metal to paramagnetic insulator transition in LaSrMnO thin films studied by X-ray magnetic circular dichroism

Shibata, Goro*; Yoshimatsu, Kohei*; Sakai, Enju*; Singh, V. R.*; Verma, V.*; Ishigami, Keisuke*; Harano, Takayuki*; Kadono, Toshiharu*; Takeda, Yukiharu; Okane, Tetsuo; et al.

Physical Review B, 89(23), p.235123_1 - 235123_5, 2014/06

AA2015-0419.pdf:0.33MB

https://doi.org/10.1103/PhysRevB.89.235123

Electronic structures of N-doped graphene with native point defects

Hou, Z.*; Wang, X.*; Ikeda, Takashi; Terakura, Kiyoyuki*; Oshima, Masaharu*; Kakimoto, Masaaki*

Physical Review B, 87(16), p.165401_1 - 165401_16, 2013/04

https://doi.org/10.1103/PhysRevB.87.165401

We have performed the DFT calculations to study the electronic structures of N-doped graphene with vacancies and Stone-Wales defect. Our results show that monovacancies in graphene act as hole dopants and that two substitutional N dopants are needed to compensate for the hole introduced by a monovacancy. On the other hand, divacancy does not produce any free carriers. Interestingly, a single N dopant at divacancy acts as an acceptor rather than a donor. Compared with the case of an isolated N dopant in perfect graphene, the electrons donated by substitutional N dopants would be localized significantly when a N-N pair is formed. The N-N interaction and the interference between native point defect and N dopant strongly modify the role of N doping regarding the free carrier production in the bulk bands. Our results are qualitatively consistent with the experimental observation that the concentration of free electrons introduced by N dopants would be lower than that of doped N.

Theoretical characterization of X-ray absorption, emission, and photoelectron spectra of nitrogen doped along graphene edges

Wang, X.*; Hou, Z.*; Ikeda, Takashi; Oshima, Masaharu*; Kakimoto, Masaaki*; Terakura, Kiyoyuki*

Journal of Physical Chemistry A, 117(3), p.579 - 589, 2013/01

https://doi.org/10.1021/jp307405r

-edge X-ray absorption (XAS), emission (XES), and photoelectron (XPS) spectra of nitrogen doped along graphene edges are systematically investigated by using first-principles methods. In this study we considered pyridinium-like, pyridine-like, cyanide-like, and aminelike nitrogens at armchair and zigzag edges and pyrrole-like nitrogen at armchair edge as well as graphite-like nitrogen at graphene interior site. Our results indicate that nitrogen configuration and its location (armchair or zigzag edge) in nitrogen-doped graphene can be identified via the spectral analysis. Furthermore, some controversial spectral features observed in experiment for N-doped graphene-like materials are unambiguously assigned. The present analysis gives an explanation to the reason why the peak assignment is usually made differently between XPS and XAS.

Indirect contribution of transition metal towards oxygen reduction reaction activity in iron phthalocyanine-based carbon catalysts for polymer electrolyte fuel cells

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

Electrochimica Acta, 74, p.254 - 259, 2012/07

https://doi.org/10.1016/j.electacta.2012.04.075

The electronic structure of the residual metal atoms in FePc-based carbon catalysts, prepared by pyrolyzing a mixture of FePc and phenolic resin polymer at 800C, before and after acid washing have been investigated using XAFS spectroscopy to clarify the role of Fe in the ORR activity. The decomposition analyses for the XAFS spectra reveal that the composition ratio of each Fe component is unaltered by the acid washing, indicating that the residual Fe components were removed by the acid washing irrespective of their chemical states. Because the oxygen reduction potential was approximately unchanged by the acid washing, the residual Fe itself does not seem to contribute directly to the ORR activity. The residual Fe can act as a catalyst to accelerate the growth of the sp carbon network during pyrolysis. The results imply that light elements are components of the ORR active sites in the FePc-based carbon catalysts.

Interplay between nitrogen dopants and native point defects in graphene

Hou, Z.*; Wang, X.*; Ikeda, Takashi; Terakura, Kiyoyuki*; Oshima, Masaharu*; Kakimoto, Masaaki*; Miyata, Seizo*

Physical Review B, 85(16), p.165439_1 - 165439_9, 2012/04

https://doi.org/10.1103/PhysRevB.85.165439

To understand the interaction between nitrogen dopants and point defects in graphene, we have studied energetic stability of N-doped graphene with vacancies and Stone-Wales defect by performing the density functional theory calculations. Our results show that N substitution energetically prefers to occur at the carbon atoms near the defects, especially for those sites with larger bond shortening, indicating that the defect-induced strain plays an important role in the stability of N dopants. In the presence of mono-vacancy, the most stable position for N is the pyridine-like configuration while for other point defects studied N prefers a site in the pentagonal ring. While the N doping is endothermic in defect-free graphene, it becomes exothermic for defective one. Our results imply that the point defect and N dopant attract each other, which means that substitutional N dopants would increase the probability of point defect generation and vice versa.

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.

-H2AX and phosphorylated ATM focus formation in cancer cells after laser plasma X irradiation

Sato, Katsutoshi; Nishikino, Masaharu; Okano, Yasuaki*; Oshima, Shinsuke*; Hasegawa, Noboru; Ishino, Masahiko; Kawachi, Tetsuya; Numasaki, Hodaka*; Teshima, Teruki*; Nishimura, Hiroaki*

Radiation Research, 174(4), p.436 - 445, 2010/10

https://doi.org/10.1667/RR2178.1

Usefulness of laser-plasma X-ray pulse for medical and radiation biological studies was investigated and compared with that of conventional sources such as those obtained from a linear accelerator. A cell irradiation system was developed which uses Copper-K (8 keV) lines from an ultra-short high intensity laser to produce plasma. The absorbed dose of the 8 keV laser-plasma X-ray pulse was accurately estimated with Gafchromic EBT film. When the cells were irradiated with approximately 2 Gy of laser plasma X-ray, the circular regions on -H2AX positive cells could be clearly identified. Moreover, the number of -H2AX and phosphorylated ataxia telangiectasia mutated (ATM) foci induced by 8 keV laser plasma X-ray were comparable to those induced by 4MV X-ray. These results indicate that the laser plasma X-ray source can be useful for radiation biological studies.