Activity enhancement of platinum oxygen-reduction electrocatalysts using ion-beam induced defects

Kimata, Tetsuya*; Kakitani, Kenta*; Yamamoto, Shunya*; Shimoyama, Iwao; Matsumura, Daiju; Iwase, Akihiro*; Mao, W.*; Kobayashi, Tomohiro*; Yamaki, Tetsuya*; Terai, Takayuki*

Physical Review Materials (Internet), 6(3), p.035801_1 - 035801_7, 2022/03

https://doi.org/10.1103/PhysRevMaterials.6.035801

Improvement of HI concentration performance for hydrogen production iodine-sulfur process using crosslinked cation-exchange membrane

Tanaka, Nobuyuki; Sawada, Shinichi*; Yamaki, Tetsuya*; Kodaira, Takahide*; Kimura, Takehiro*; Nomura, Mikihiro*

Chemical Engineering Science, 237, p.116575_1 - 116575_11, 2021/06

https://doi.org/10.1016/j.ces.2021.116575

We have been developing the ion exchange membranes by a radiation grafted polymerization method to improve HI concentration performance for Electro-electrodialysis (EED) in the thermochemical water-splitting hydrogen production iodine-sulfur process. In this work, the crosslinking structures were introduced to the ion exchange membranes. The proton conductivity (), transport number (t), and water permeation factor () of these crosslinked ion exchange membranes were measured and the effect of crosslinks to these performance indexes were investigated. The introduction of crosslinks was found to improve the selectivity of H and water transport (increase of t and decrease of ), although the somewhat decreased. The EED model that we established to discuss the permeation mechanism of EED system was used to theoretically analyze the effect of crosslink on the performance indexes. Based on this analysis of measurement results, the introduction of the crosslink was found to little affect the absorbed amount of HIx solution and H diffusion coefficient in the tested membranes, whereas it could lead to decrease I diffusion coefficient. The results of and t could reflect these effects. In addition, we found the fact that crosslink can inhibit the swelling due to the absorption of the HIx solution. As a result, the value decreased owing to the introduction of crosslink.

Changes in electronic structure of carbon supports for Pt catalysts induced by vacancy formation due to Ar irradiation

Okazaki, Hiroyuki*; Kakitani, Kenta*; Kimata, Tetsuya*; Idesaki, Akira*; Koshikawa, Hiroshi*; Matsumura, Daiju; Yamamoto, Shunya*; Yamaki, Tetsuya*

Journal of Chemical Physics, 152(12), p.124708_1 - 124708_5, 2020/03

https://doi.org/10.1063/1.5144568

FE-SEM observation of chains of nanohillocks in SrTiO and Nb-doped SrTiO surfaces irradiated with swift heavy ions

Kitamura, Akane; Ishikawa, Norito; Kondo, Keietsu; Yamamoto, Shunya*; Yamaki, Tetsuya*

Nuclear Instruments and Methods in Physics Research B, 460, p.175 - 179, 2019/12

https://doi.org/10.1016/j.nimb.2019.01.037

Irradiation at grazing incidence formed chains of multiple hillocks on the surface of strontium titanate (SrTiO) and titanium oxide (TiO). They were observed with an atomic force microscope (AFM), however, the AFM measurement gives resolution errors in a nanometer order due to the curvature of the probe tip. To prevent these errors, a field emission scanning electron microscope (FE-SEM) would be a better option for observation. In this study, we performed SEM observations for the chains of the multiple hillocks. Single crystals of SrTiO and TiO were irradiated with 200 MeV Xe in the tandem accelerator at JAEA-Tokai. It was revealed that a lot of isolated hillocks were formed in a line on these surface. The diameter and the interval of those hillocks are discussed in comparison to AFM observation.

Effect of HIx solution concentration on ion-exchange membrane performance in electro-electrodialysis

Tanaka, Nobuyuki; Yamaki, Tetsuya*; Asano, Masaharu*; Terai, Takayuki*

Journal of Membrane Science, 587, p.117171_1 - 117171_9, 2019/10

https://doi.org/10.1016/j.memsci.2019.117171

Electro-electrodialysis (EED) has been applied to thermochemical water-splitting iodine-sulfur process for hydrogen production in order to enhance the HI component in the HI-I-HO mixture (HIx solution). In this paper, HIx solution concentration dependence of the conductivity () and transport number () as the membrane-performance indexes of Nafion 212 and a styrene-grafted poly(ethylene-co-tetrafluoroethylene) (ETFE) membrane was experimentally investigated. From the theoretical analysis for the measurements based on the new EED model, the effects of the H and I content and the diffusion coefficients of H and I in the evaluated membranes on and were as follows: HIx solution concentration dependence of ion contents exhibited a significantly small or different variation in comparison with that of and t, which indicates that the dominant factors for and would not be ion contents; thereby, the effect of ion diffusion coefficients should not be ruled out. For of Nafion 212, H diffusion is the dominant factor because the existence of I was negligible, whereas for the ETFE-St membrane, the effect of I diffusion should be considered. I diffusion could more strongly affect for the evaluated membranes rather than H diffusion, which indicates that H selectivity of the membranes could be relatively determined by the variation of the I behavior in the membranes.

Development of cation and anion exchange membranes for saline water concentration using high-energy heavy-ion beams

Sawada, Shinichi*; Yasukawa, Masahiro*; Koshikawa, Hiroshi*; Kitamura, Akane; Higa, Mitsuru*; Yamaki, Tetsuya*

Nihon Kaisui Gakkai-Shi, 73(4), p.208 - 216, 2019/08

For applications to saline water concentration by electrodialysis, we prepared nano-structure-controlled cation and anion exchange membranes (CEMs and AEMs) by a so-called ion-track grafting technique. This new technique involves irradiation of a polymer substrate with an MeV-GeV heavy-ion beam to form the nano-sized cylindrical ion tracks and the graft polymerization only into the ion tracks for the creation of one-dimensional transport pathways. A 25-m-thick poly(ethylene-co-tetrafluoroethylene) film was irradiated with 560 MeV Xe or 310 MeV Kr. The irradiated films were immersed in grafting solutions of ethyl p-styrenesulfonate (EtSS) and chloromethylstyrene (CMS), and then subjected to the hydrolysis of EtSS units and quaternization of CMS units to prepare CEMs and AEMs, respectively. These CEMs and AEMs showed lower resistance than the commercially-available membranes even at the very low water uptake. This would be due to the signifcantly-effcient transport of ions through the unique one-dimensional highly-connected transport pathways. In the saline water concentration experiment, a pair of our CEM and a commercial AEM or vice versa led to a higher salt concentration in the concentration chamber than did a pair of the commercial membranes. This result demonstrated great applicability of our ion-track-grafted CEMs and AEMs for saline water concentration.

FE-SEM observations of multiple nanohillocks on SrTiO irradiated with swift heavy ions

Kitamura, Akane; Ishikawa, Norito; Kondo, Keietsu; Fujimura, Yuki; Yamamoto, Shunya*; Yamaki, Tetsuya*

Transactions of the Materials Research Society of Japan, 44(3), p.85 - 88, 2019/06

https://doi.org/10.14723/tmrsj.44.85

Swift heavy ions can create nanosized hillocks on the surfaces of various ceramics. When these materials are irradiated with swift heavy ions at normal incidence, each ion impact results in the formation of a single hillock on the surfaces. In contrast, irradiation at grazing incidence forms chains of multiple hillocks on the surface, for example, for strontium titanate (SrTiO). So far, chains of multiple hillocks have been investigated using atomic force microscopy (AFM). It should be noted that AFM measurements involve systematic errors of several nanometers due to the finite size of the probe tip. Consequently, it is possible that the image of one hillock may merge with that of a neighboring hillock even if the two hillocks are well separated. In contrast to AFM, field-emission scanning electron microscopy (FE-SEM) is a useful technique for obtaining higher-resolution images. In this study, we observed multiple nanohillocks on the surfaces of SrTiO using FE-SEM. Crystals of SrTiO(100) and 0.05 wt% Nb-doped SrTiO(100) were irradiated with 350 MeV Xe ions, respectively, at grazing incidence, where the angle between the sample surface and the beam was less than 2. On the SrTiO surface, a chain of periodic nanohillocks is created along the ion path. In contrast, black lines accompanied by hillocks are observed on the Nb-doped SrTiO surface.

Fluoropolymer-based nanostructured membranes created by swift-heavy-ion irradiation and their energy and environmental applications

Yamaki, Tetsuya*; Nuryanthi, N.*; Kitamura, Akane; Koshikawa, Hiroshi*; Sawada, Shinichi*; Voss, K.-O.*; Severin, D.*; Tautmann, C.*

Nuclear Instruments and Methods in Physics Research B, 435, p.162 - 168, 2018/11

https://doi.org/10.1016/j.nimb.2018.03.021

We used individual single-ion tracks in fluoropolymers with diameters of tens to hundreds of nanometers; chemical etching and ion-track grafting enabled us to develop ion-track and proton-conductive membranes, respectively. In the ion-track membranes of PVDF, strongly-LET-dependent etching was found, so the pore shape as well as the size was exclusively controlled by the track structures. We performed the ion-track grafting of styrene into ETFE to develop nanostructure-controlled proton exchange membranes (PEMs) for applications in PEM fuel cells. Our ion beam technology to develop fluoropolymer-based nanostructures has the potential to apply in the field of filtration processes and fuel cell devices. This would make it possible to provide new microfiltration technology for water treatment, sterilization, petroleum refining and dairy processing.

Analysis of scintillation light intensity by microscopic radiation transport calculation and Frster quenching model

Ogawa, Tatsuhiko; Yamaki, Tetsuya*; Sato, Tatsuhiko

PLOS ONE (Internet), 13(8), p.e0202011_1 - e0202011_19, 2018/08

https://doi.org/10.1371/journal.pone.0202011

Scintillators are generally used to detect various kinds of particles such as electrons, gammas, protons and heavy ions. Scintillators emit photons according to the energy deposited to the crystal. It is also known that light yield is suppressed for particles depositing energy densely owing to quenching. Moreover, it is suggested that quenching is attributed to transfer of energy from excited fluorescent molecules to damaged molecules (Frster mechanism). In this study, energy deposition in a scintillator crystal by radiation was calculated using radiation transport codes to finally obtain excitation and damage of fluorescent molecules. Based on the calculation, spatial configuration of exited and damaged molecules. Then the probability that Frster mechanism takes place in excited molecules were estimated to obtain the number of fluorescent molecules that emit photons. As a result, light yield is proportionally increased with increase in the incident energy in case of electron incidence. On the other hand, light yield is increased non-linearly in case of proton incidence. This trend is in a good agreement with the experimental results.

Prediction of scintillation light yield based on sub-micrometer radiation transport calculation and Frster effect

Ogawa, Tatsuhiko; Yamaki, Tetsuya*; Sato, Tatsuhiko

QST-M-8; QST Takasaki Annual Report 2016, P. 34, 2018/03

https://repo.qst.go.jp/records/73811

Scintillators are used for detection of various radiation such as electrons, -rays, protons and heavy ions. Fundamentally, scintillators emit lights depending on the deposition energy, but light yield is suppressed (i.e., quenching) in case of highly ionizing radiation. In this study, light yield of scintillators was calculated based on following assumptions; scintillation is attributed to excitation of phosphor molecules by incident particles, Frster effect by the damaged phosphor molecules is the mechanism responsible for quenching, and excitation and damage of phosphor molecules can be calculated by molecular-scale radiation transport simulation code RITRACKS. Protons from 0.1 MeV to 150 MeV and electrons from 0.1 MeV to 1 MeV were directed to full-stop thick NE102 scintillator as incident particles and the light yield of scintillators was calculated. Both calculated light yields and earlier measurement data showed that the light yield by electrons is proportional to incident energy whereas the light yield by protons increases with increase in incident energy in a non-linearly. Thus the simulation in this study can accurately reproduce the light yield of scintillators in radiation detection.