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Journal Articles

Development of a radiation tolerant laser-induced breakdown spectroscopy system using a single crystal micro-chip laser for remote elemental analysis

Tamura, Koji; Nakanishi, Ryuzo; Oba, Hironori; Karino, Takahiro; Shibata, Takuya; Taira, Takunori*; Wakaida, Ikuo

Journal of Nuclear Science and Technology, 8 Pages, 2024/00

https://doi.org/10.1080/00223131.2023.2298485
 Times Cited Count：0 Percentile：0.01(Nuclear Science & Technology)

Journal Articles

Dispersive XAFS Study on the Laser-Induced Reduction of a Rh$$^{3+}$$ ion complex; Presence of a Rh$$^{+}$$ Intermediate in Direct Photoreduction

Saeki, Morihisa*; Matsumura, Daiju; Nakanishi, Ryuzo*; Yomogida, Takumi; Tsuji, Takuya; Saito, Hiroyuki*; Oba, Hironori*

Journal of Physical Chemistry C, 126(12), p.5607 - 5616, 2022/03

https://doi.org/10.1021/acs.jpcc.1c10160
 Times Cited Count：1 Percentile：14.66(Chemistry, Physical)

The reaction mechanism of the direct photoreduction of a Rh$$^{3+}$$ ion complex to a Rh$$^{0}$$ species induced by pulsed ultraviolet laser irradiation was studied using dispersive X-ray absorption fine structure (DXAFS) spectroscopy. The time-resolved X-ray absorption near edge structure (XANES) showed the absence of isosbestic points and suggested that more than two Rh$$^{n+}$$ species contribute toward the direct photoreduction of Rh$$^{3+}$$. Analysis of the time-resolved XANES data by singular value deposition showed that the direct photoreduction involves three Rh$$^{n+}$$ species. Multivariate curve resolution by alternating least-squares analysis (MCR-ALS) of the time-resolved XANES data gave pure spectra and concentration profiles of the three Rh$$^{n+}$$ species. The Rh$$^{n+}$$ species were assigned to Rh$$^{3+}$$, Rh$$^{+}$$, and Rh$$^{0}$$ species based on the features of the pure XANES spectra. The concentration profiles suggested that the direct photoreduction proceeds in the order of Rh$$^{3+}$$ $$rightarrow$$ Rh$$^{+}$$ $$rightarrow$$ Rh$$^{0}$$. A reaction mechanism, which was proposed involving photoreductions of Rh$$^{3+}$$ and Rh$$^{+}$$, photoinduced autocatalytic reductions of Rh$$^{3+}$$ and Rh$$^{+}$$, and photooxidation of Rh$$^{+}$$, well reproduced the concentration profiles of three Rh$$^{n+}$$ species.

Journal Articles

Highly sensitive detection of sodium in aqueous solutions using laser-induced breakdown spectroscopy with liquid sheet jets

Nakanishi, Ryuzo; Oba, Hironori; Saeki, Morihisa; Wakaida, Ikuo; Tanabe, Rie*; Ito, Yoshiro*

Optics Express (Internet), 29(4), p.5205 - 5212, 2021/02

https://doi.org/10.1364/OE.415308
 Times Cited Count：13 Percentile：83.13(Optics)

Laser-induced breakdown spectroscopy (LIBS) combined with liquid jets was applied to the detection of trace sodium (Na) in aqueous solutions. The sensitivities of two types of liquid jets were compared: a liquid cylindrical jet with a diameter of 500 $$mu$$m and a liquid sheet jet with a thickness of 20 $$mu$$m. Compared with the cylindrical jet, the liquid sheet jet effectively reduced the splash from the laser-irradiated surface and produced long-lived luminous plasma. The limit of detection (LOD) of Na was determined to be 0.57 $$mu$$g/L for the sheet jet and 10.5 $$mu$$g/L for the cylindrical jet. The LOD obtained for the sheet jet was comparable to those obtained for commercially available inductively coupled plasma emission spectrometers.

Journal Articles

Application of an augmentation method to MCR-ALS analysis for XAFS and Raman data matrices in the structural change of isopolymolybdates

Saeki, Morihisa*; Yomogida, Takumi; Matsumura, Daiju; Saito, Takumi*; Nakanishi, Ryuzo*; Tsuji, Takuya; Oba, Hironori*

Analytical Sciences, 36(11), p.1371 - 1378, 2020/11

https://doi.org/10.2116/analsci.20P147
 Times Cited Count：2 Percentile：10(Chemistry, Analytical)

We measured X-ray absorption fine structure (XAFS) and Raman spectra of isopolymolybdates(VI) in HNO$$_{3}$$ solution (0.15- 4.0 M), which change their geometries depending on acid concentration, and performed simultaneous resolution of the XAFS and Raman data using a multivariate curve resolution by alternating least-squares (MCR-ALS) analysis. In iterative ALS optimization, initial data matrices were prepared by two different methods. The MCR-ALS result of single XAFS data matrix shows large dependence on the preparation method of the initial data matrices. The MCR-ALS result of an augmented matrix of Raman and XAFS data has little dependence on the initial data matrices. It indicates that the augmentation method effectively improves the rotation ambiguities in the MCR-ALS analysis of the XAFS data. Based on the model fitting of the pure EXAFS oscillations, we revealed the change of [Mo$$_{36}$$O$$_{112}$$(H$$_{2}$$O)$$_{16}$$]$$^{2+}$$ $$rightarrow $$ [Mo$$_{2}$$O$$_{5}$$(H$$_{2}$$O)$$_{6}$$]$$^{2+}$$ $$rightarrow $$ [HMoO$$_{3}$$(H$$_{2}$$O)$$_{3}$$]$$^{+}$$ in the highly concentrated HNO$$_{3}$$ solution.

Oral presentation

Speciation of isopolymolybdate(VI) in a highly concentrated HNO$$_{3}$$ solution by Raman and EXAFS spectroscopies

Saeki, Morihisa*; Yomogida, Takumi; Matsumura, Daiju; Saito, Takumi*; Nakanishi, Ryuzo*; Tsuji, Takuya; Okamoto, Yoshihiro; Oba, Hironori*

no journal, , 

Speciation of isopolymolybdates in a highly concentrated HNO$$_{3}$$ solution was investigated by Raman spectroscopy and Mo K-edge extended X-ray absorption fine structure (EXAFS). A series of Raman spectra and EXAFS oscillations were analyzed using Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS). The MCR-ALS analysis gives us the fraction profile in change of [Mo$$_{36}$$O$$_{112}$$(H$$_{2}$$O)$$_{16}$$]$$^{8-}$$$$rightarrow$$[Mo$$_{2}$$O$$_{5}$$]$$^{2+}$$$$rightarrow$$[MoO$$_{2}$$]$$^{2+}$$ with the increase of the HNO$$_{3}$$ concentration.

Oral presentation

In Situ Time-Resolved XAFS Studies on Laser-Induced Particle Formation of Platinum Groups Metal Ions in a H$$_{2}$$O / EtOH Solution

Saeki, Morihisa*; Matsumura, Daiju; Yomogida, Takumi; Taguchi, Tomitsugu*; Tsuji, Takuya; Saito, Hiroyuki*; Nakanishi, Ryuzo*; Oba, Hironori*

no journal, , 

When nanosecond pulsed UV laser is irradiated into a H$$_{2}$$O / EtOH solution of platinum group metal (PGM) ions, PGM particles with sub-micron size are formed. We investigated laser induced particle formation of Pd$$^{2+}$$ in the H$$_{2}$$O / EtOH solution by in situ time-resolved XAFS spectroscopy and showed dependence of the reaction rate of laser-induced particle formation on the laser fluence. The dependence on the laser fluence elucidated that the photons contribute not only to the reduction of the Pd$$^{2+}$$, but also to the autocatalytic growth of the Pd particles.

Oral presentation

In situ time-resolved XAFS studies on photo-induced particle formation in an aqueous/ethanol solution of PdCl$$_{4}$$$$^{2-}$$ using ns pulsed UV laser; Dependence of chemical kinetics on laser pulse energy

Saeki, Morihisa*; Yomogida, Takumi; Matsumura, Daiju; Nakanishi, Ryuzo*; Taguchi, Tomitsugu*; Tsuji, Takuya; Saito, Hiroyuki*; Oba, Hironori*

no journal, , 

In the absence of a photoactivator, the laser-induced particle formation in an H$$_{2}$$O/ EtOH solution of PdCl$$_{4}$$$$^{2-}$$ was performed by three kinds of irradiation condition using fourth harmonics of the pulsed UV laser (266 nm). In the irradiation, pulsed laser energy was arranged to 5, 10 and 25 mJ, where average laser power is kept to 250 mW. The reaction kinetics of the laser-induced particle formation was observed using dispersive XAFS measurement. About half of Pd ions were reduced with 5 mJ pulsed laser irradiation. In contrast, all Pd ions were reduced with 25 mJ pulsed laser irradiation. The result elucidates that the laser photon contributes to the generation of Pd metals by the multi-photon process.

Oral presentation

Practical application of LIBS and rerated spectroscopy for decommissioning work of Fukushima Daiichi Nuclear Power Station

Wakaida, Ikuo; Oba, Hironori; Miyabe, Masabumi; Akaoka, Katsuaki; Oba, Masaki; Tamura, Koji; Saeki, Morihisa; Nakanishi, Ryuzo; Ikeda, Yuji*; Sakka, Tetsuo*; et al.

no journal, , 

no abstracts in English

Oral presentation

Gamma-ray irradiation effects to the laser-induced breakdown spectroscopy system using a ceramic and a single crystal micro-laser

Tamura, Koji; Nakanishi, Ryuzo; Oba, Hironori; Saeki, Morihisa; Taguchi, Tomitsugu*; Lim, H. H.*; Taira, Takunori*; Wakaida, Ikuo

no journal, , 

Oral presentation

Rare earth elements detection in mixed oxide using a fiber optic LIBS with a ceramic micro-laser

Oba, Hironori; Tamura, Koji; Nakanishi, Ryuzo; Saeki, Morihisa; Lim, H. H.*; Taira, Takunori*; Wakaida, Ikuo

no journal, , 

Oral presentation

Development on laser remote analysis for on-site, in-situ and quick screening of nuclear fuel debris in decommissioning of Fukushima Daiichi Nuclear Power Station

Wakaida, Ikuo; Oba, Hironori; Miyabe, Masabumi; Akaoka, Katsuaki; Oba, Masaki; Tamura, Koji; Saeki, Morihisa; Nakanishi, Ryuzo; Ikeda, Yuji*; Sakka, Tetsuo*; et al.

no journal, , 

Oral presentation

DXAFS study on laser-induced photoreduction mechanism of Rh$$^{III}$$ ion complexes; Extraction of intermediates information by multivariate spectral analysis

Saeki, Morihisa*; Matsumura, Daiju; Nakanishi, Ryuzo*; Yomogida, Takumi; Tsuji, Takuya; Saito, Hiroyuki*; Oba, Hironori*

no journal, , 

The precious metal (PM) ions complexed with negative ions and water molecules in solution has a charge transfer absorption band in the UV region. When alcohol is added to such a PM$$^{n+}$$ complex solution and irradiated with an ultraviolet laser, the PM$$^{n+}$$ complex is electronically excited and reacts with the alcohol to be reduced to the neutral atom PM$$^{0}$$. The reduced PM$$^{0}$$ spontaneously aggregates in the solution to form fine particles. This process is called Laser-Induced Particle Formation (LIPF), and is used for the formation of precious metal nanoparticles and the recovery of precious metals from factory effluents. We have investigated the LIPF reaction mechanism of Rh$$^{3+}$$ ion complexes by in situ energy-dispersive X-ray absorption fine structure spectroscopy(XAFS). As a result of analyzing the obtained XAFS spectra, we found that Rh species with three oxidation numbers are involved in the Rh$$^{3+}$$reduction reaction, which proceeds from Rh$$^{3+}$$ to Rh$$^{int}$$ (intermediate) to Rh$$^{0}$$.

Oral presentation

Preparation for trial use of optical fiber based portable LIBS system at actual working site in decommissioning of Fukushima Daiichi Nuclear Power Station

Wakaida, Ikuo; Oba, Hironori; Nakanishi, Ryuzo; Akaoka, Katsuaki; Shibata, Takuya

no journal, , 

Oral presentation

Laser remote analysis for decommissioning of Fukushima Daiichi Nuclear Power Station

Wakaida, Ikuo; Oba, Hironori; Akaoka, Katsuaki; Shibata, Takuya; Nakanishi, Ryuzo; Karino, Takahiro

no journal, , 

no abstracts in English

Oral presentation

Laser remote analysis for decommissioning of Fukushima Daiichi Nuclear Power Station (1FNPS) and its application in the actual site

Wakaida, Ikuo; Oba, Hironori; Nakanishi, Ryuzo; Akaoka, Katsuaki; Shibata, Takuya

no journal, , 

Oral presentation

Laser remote analysis for decommissioning of Fukushima Daiichi Nuclear Power Station (FDNPS) and its application for radioactive sampled materials

Wakaida, Ikuo; Oba, Hironori; Nakanishi, Ryuzo; Akaoka, Katsuaki; Shibata, Takuya; Karino, Takahiro

no journal, , 

Oral presentation

Dispersive XAFS study on the laser-induced reduction of a Rh$$^{3+}$$ ion complex in a H$$_{2}$$O/EtOH solution

Saeki, Morihisa*; Matsumura, Daiju; Nakanishi, Ryuzo*; Yomogida, Takumi; Tsuji, Takuya; Saito, Hiroyuki*; Oba, Hironori*

no journal, , 

The reaction mechanism of the direct photo-reduction of a Rh$$^{3+}$$ ion complex to a Rh$$^{0}$$ species was studied using dispersive X-ray absorption fine structure spectroscopy. The time-resolved X-ray absorption near edge structure (XANES) showed the absence of isosbestic points. It suggested that more than two Rhn+ species contribute toward the reaction. We applied singular value deposition to the time-resolved XANES data and showed the contribution of three Rh$$^{n+}$$ species to the direct photoreduction. Next, in order to extract spectral information on the Rh$$^{n+}$$ intermediate, we analyzed the time-resolved XANES data using multivariate curve resolution analysis, which gives pure spectra and concentration profile of the Rh$$^{n+}$$ species. Finally, based on feature of the pure spectrum, we assigned the Rh$$^{n+}$$ intermediate to the Rh$$^{n+}$$ species.

Oral presentation

Laser remote analysis by optical fiber coupled laser induced breakdown spectroscopy for on-site, in-situ screening of nuclear debris in decommissioning of Fukushima Daiichi Nuclear Power Station

Wakaida, Ikuo; Oba, Hironori; Akaoka, Katsuaki; Nakanishi, Ryuzo; Shibata, Takuya; Karino, Takahiro

no journal, , 

Oral presentation

Research and development of laser remote analysis for decommissioning of Fukushima Daiichi Nuclear Power Station

Wakaida, Ikuo; Oba, Hironori; Akaoka, Katsuaki; Shibata, Takuya; Nakanishi, Ryuzo; Karino, Takahiro; Sakamoto, Kan*; Ikeda, Yuji*; Taira, Takunori*

no journal, , 

no abstracts in English

Oral presentation

Comparison of radiation effects for a ceramics and a single crystal microchip of a Laser-Induced Breakdown Spectroscopy (LIBS) system for remote analysis

Tamura, Koji; Nakanishi, Ryuzo; Oba, Hironori; Wakaida, Ikuo

no journal, , 

29 (Records 1-20 displayed on this page)