Dispersive XAFS Study on the Laser-Induced Reduction of a Rh 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

The reaction mechanism of the direct photoreduction of a Rh ion complex to a Rh 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 species contribute toward the direct photoreduction of Rh. Analysis of the time-resolved XANES data by singular value deposition showed that the direct photoreduction involves three Rh 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 species. The Rh species were assigned to Rh, Rh, and Rh species based on the features of the pure XANES spectra. The concentration profiles suggested that the direct photoreduction proceeds in the order of Rh Rh Rh. A reaction mechanism, which was proposed involving photoreductions of Rh and Rh, photoinduced autocatalytic reductions of Rh and Rh, and photooxidation of Rh, well reproduced the concentration profiles of three Rh species.

Radiation dose rate effects on the properties of a laser-induced breakdown spectroscopy system developed using a ceramics micro-laser for fiber-optic remote analysis

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

Journal of Nuclear Science and Technology, 58(4), p.405 - 415, 2021/04

https://doi.org/10.1080/00223131.2020.1854880

Radiation dose rate effects on the properties of a compact fiber-optic laser-induced breakdown spectroscopy (LIBS) system with a monolithic Nd:YAG/Cr:YAG composite ceramics were investigated for remote analysis in hazardous environment. To investigate radiation effects on the LIBS signal, properties related to the Nd:YAG laser operation such as oscillation threshold, output energy, oscillation timing, temporal pulse shape, and beam profile were measured as a function of the radiation dose rate from 0 to 10 kGy/hr in view of their influences to the signal. LIBS spectra of zirconium metal were measured under irradiation. Although signal intensity decreased considerably by irradiation, informative spectra were well obtained even at the maximum radiation dose rate. From the comparison of the LIBS-related parameters among the laser properties, signal reduction was mainly ascribed to the pulse energy reduction. Scintillation emission spectra were also measured from the ceramics during the irradiation, where the signal intensity increased linearly with the dose rate. The results show that the developed system.

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

We measured X-ray absorption fine structure (XAFS) and Raman spectra of isopolymolybdates(VI) in HNO 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 [MoO(HO)] [MoO(HO)] [HMoO(HO)] in the highly concentrated HNO solution.

In Situ Time-Resolved XAFS Studies on Laser-induced Particle Formation of Palladium Metal in an Aqueous/EtOH solution

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

Journal of Physical Chemistry C, 123(1), p.817 - 824, 2019/01

https://doi.org/10.1021/acs.jpcc.8b09532

Reaction kinetics of laser-induced particle formation in an aqueous solution of PdCl was investigated by transmission electron microscope (TEM) and dispersive X-ray absorption fine structure (DXAFS). The Pd particle was generated by irradiation of nanosecond pulsed 266-nm laser. The TEM observation showed dependence of the particle size on the laser fluence and promotion of the particle growth by irradiation of high-fluence laser. The DXAFS data give us the Pd concentration. Temporal changes of the Pd concentration analyzed based on Finke-Watzky two step mechanism. The analysis elucidates that the laser photon contributes to the reduction of the PdCl ion by the one-photon process and to the autocatalytic growth of the Pd particles by the multi-photon process.

Development of separation technique for platinum group metals from radioactive liquid waste utilizing laser-induced particulate formation

Saeki, Morihisa*; Asai, Shiho; Oba, Hironori*

Bunseki, 2018(4), p.138 - 143, 2018/04

Platinum group metal (PGM) has attracted much attention in light of increasing demands in the industrial sector. A wide variety of techniques specialized for PGM separation, such as, solvent extraction, solid phase extraction, and molten salt electrolysis have been developed so far. Among such techniques, a newly developed separation technique based on laser-induced particulate formation can be a promising alternative to conventional ones. It enables non-contact and highly-selective separation with a simple operation. In this review, the research history and the basic mechanism of laser-induced particulate formation were outlined. Several applications were also mentioned, focusing on our latest research progress which achieved a world first quantitation of radioactive palladium in a spent nuclear fuel sample.

Study on laser-induced particle formation of palladium ion by time-resolved X-ray spectroscopy

Saeki, Morihisa*; Taguchi, Tomitsugu*; Oba, Hironori*; Matsumura, Daiju; Tsuji, Takuya; Yomogida, Takumi

Denki Gakkai Kenkyukai Shiryo, Denshi Zairyo Kenkyukai (EFM-17-010021), p.15 - 18, 2017/09

Irradiation of nanosecond pulsed UV laser into a solution of palladium ion leads to formation of palladium particles with sub-micron size particles by time-resolved X-ray absorption spectroscopy.

Wet separation between palladium(II) and molybdenum(IV) ions by using laser-induced particle formation; Enhancement of recovery efficiency of palladium by laser condition

Saeki, Morihisa; Taguchi, Tomitsugu; Nakashima, Nobuaki*; Oba, Hironori

Journal of Photochemistry and Photobiology A; Chemistry, 299, p.189 - 193, 2015/02

https://doi.org/10.1016/j.jphotochem.2014.11.022

Effect of liquid-sheet thickness on detection sensitivity for laser-induced breakdown spectroscopy of aqueous solution

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

Optics Express (Internet), 22(20), p.24478 - 24490, 2014/10

https://doi.org/10.1364/OE.22.024478

For aqueous-solution-based elemental analysis, we used a thin liquid sheet (m-scale thickness) in laser-induced breakdown spectroscopy with nanosecond laser pulses. Laser-induced plasma is emitted by focusing a pulsed Nd:YAG laser (1064 nm) on a 5- to 80-m-thick liquid sheet in air. To optimize the conditions for detecting elements, we studied how the signal-to-background ratio (SBR) for H Balmer and Na-neutral emission lines depends on the liquid-sheet thickness. The SBR of the H Balmer and Na-neutral lines was maximized for a sheet thickness of 20 m at the laser energy of 100 mJ. The hydrodynamics of liquid flow induced by the laser pulse was analyzed by laser flash shadowgraph imaging. Time-resolved observation of the hydrodynamics and plasma emission suggests that the dependence of the SBR on the liquid-sheet thickness is correlated with the volume of flowing liquid that interacts with the laser pulses.

Development of radiation-resistant optical fiber for application to observation and laser spectroscopy under high radiation dose

Ito, Chikara; Naito, Hiroyuki; Nishimura, Akihiko; Oba, Hironori; Wakaida, Ikuo; Sugiyama, Akira; Chiyatani, Keiji

Journal of Nuclear Science and Technology, 51(7-8), p.944 - 950, 2014/07

https://doi.org/10.1080/00223131.2014.924883

In the Fukushima Daiichi Nuclear Power Station, it is necessary to survey the locations and conditions of fuel debris inside reactor pressure vessels or primary containment vessels under water and radiation environment in preparation for removing fuel debris. An optical fiber is well known for features such as signal transmission, light weight, superior insulation performance, water resistance and electromagnetic noise resistance. These features allow the optical fiber to simplify the instrumentation systems for in-vessel inspection, as long as provide that the optical fiber can be used under high radiation dose environment. The radiation resistance of an optical fiber was improved by increasing the amount of hydroxyl up to 1000 ppm in pure silica fiber. The improved optical fibers were irradiated with -ray up to 1 10 Gy using a Co source. They indicated a large peak around 600 nm and a peak tail from ultraviolet region, but no large absorption in infrared region except a hydroxyl absorption peak of 945 nm. We have confirmed that the optical fiber containing 1000 ppm hydroxyl has enough radiation resistance for radiation induced transmission losses and the infrared imaging is effective for observation under high radiation doses.

New micromachining technique for unworkable sapphire by highly coalesced ion implantation and eximer laser irradiation

Ishiyama, Shintaro; Oba, Hironori; Yamamoto, Shunya; Shobu, Takahisa

Kagaku Kogaku Rombunshu, 40(2), p.131 - 136, 2014/03

https://doi.org/10.1252/kakoronbunshu.40.131

New micromachining technique of unworkable sapphire was demonstrated by highly coalesced ion implantation and eximer laser irradiation methods. After proton implantation by 0.3 MeV H up to 110/cm into sapphire, damaged region was formed beneath 1m depth from the surface of implanted sapphire and blistering was observed by 0.33 MeV H over 110/cm. Ion implanted sapphire behaves peculiar wavelength absorption at 200 nm and ion implanted sapphire by 0.3 MeV H up to 110/cm was irradiated by ArF laser with 3.4 J/cm1 shot and micro trench shape with 1m depth and 5080 m width was observed on the surface of ion implanted sapphire. These results mean that micromachining of sapphire on the order of m width with arbitrarily depth can be possible by highly coalesced ion implantation and laser irradiation techniques.