成田 弘一*; Nicolson, R. M.*; 元川 竜平; 伊藤 文之*; 森作 員子*; 後藤 みどり*; 田中 幹也*; Heller, W. T.*; 塩飽 秀啓; 矢板 毅; et al.
Inorganic Chemistry, 58(13), p.8720 - 8734, 2019/07
Current industrial practices to extract rhodium from virgin ores carry a heavy environmental burden. Improving the efficiency of the hydrometallurgical processes to separate and recover rhodium from other precious metals provides an opportunity to improve the materials and energy balances, but the presence of mixed chloride-rhodium species following leaching by acid chloride media complicates the recovery process. In this work we have applied a broad range of analytical techniques (FT-IR spectroscopy, X-ray diffraction, EXAFS, water-transfer analysis, small-angle neutron scattering, NMR spectroscopy, and electrospray mass spectrometry), which together show that the amino-amide reagent preferentially transports chlorido-rhodium species as a 1:2 neutral assembly from aqueous 2.0 M HCl phase into an organic phase. The extractants then ligate in the outer coordination shell of the chloride-rhodium anion, making this an efficient separation process. In this study, we found that protonation to the extractants induced to form a proton chelate ring, which pre-organises the ligand to present an array of charge diffuse C-H bonds. This templated arrangement of positive dipoles favors complexation to the charge diffuse chloride-rhodium anion over the more charge-dense chloride anion.
小林 大志*; 中嶋 翔梧*; 元川 竜平; 松村 大樹; 斉藤 拓巳*; 佐々木 隆之*
Langmuir, 35(24), p.7995 - 8006, 2019/06
We report the hierarchical structure of zirconium hydroxide after aging at different temperatures to elucidate the factors governing zirconium solubility in aqueous solutions. Zirconium hydroxide solid phases after aging at 25, 40, 60, and 90C under acidic to alkaline conditions were investigated using extended X-ray absorption fine structure (EXAFS) and wide- and small-angle X-ray scattering (WAXS and SAXS) techniques to reveal the bulk and surface structures of the solid phases from the nanoscale to submicroscale. After aging at 25 C, the fundamental building unit of the solid phase was a zirconium hydroxide tetramer. The tetramers formed primary particles approximately 3 nm in size, which in turn formed aggregates hundreds of nanometers in size. This hierarchical structure was found to be stable up to 60 C under acidic and neutral conditions and up to 40 C under alkaline conditions. After aging at 90 C under acidic conditions and at 60 and 90 C under alkaline conditions, the WAXS and EXAFS measurements suggested the crystallization of the solid phase. The transformation of the solid-phase structure by temperature was discussed in relation to the solubility product to understand the solubility-limiting solid phase. The solubility of zirconium hydroxide after aging at different temperatures was governed not only by the size of the primary particles, but also by their surface configuration.
元川 竜平; 小林 徹; 遠藤 仁; Mu, J.*; Williams, C. D.*; Masters, A. J.*; Antonio, M. R.*; Heller, W. T.*; 長尾 道弘*
ACS Central Science, 5(1), p.85 - 96, 2019/01
We present a hierarchical aggregate model of an organic phase containing a coordination species that acts as a fundamental building unit of higher-order structures formed in the organic phase. We aimed to elucidate the fundamental aspects of the microscopic structure and phase separation occurring in ionic separation and recovery systems during solvent extraction. The coordination species aggregate through a hydrogen-bonding network formed by interaction between the hydrophilic part of the coordination species with extracted water and acid molecules. This reduces the hydrophilic surface area, resulting in subsequent formation of small primal clusters of 2 to 3 nm in diameter. The primal clusters further aggregate due to van der Waals interaction to form large aggregates of 10 nm in diameter. The size of the primal cluster does not depend on the concentration of the coordination species, whereas the size of the large aggregate increases as the aggregation number of the primal clusters increases. We conclude that hybrid interaction is a key driving force in the formation and growth of the hierarchical aggregate and the induction of phase separation of the organic phase.
Mu, J.*; 元川 竜平; 阿久津 和宏*; 西辻 祥太郎*; Masters, A. J.*
Journal of Physical Chemistry B, 122(4), p.1439 - 1452, 2018/02
We present evidence that the transition between organic and third phases, which is an unusual transition between two isotropic, bi-continuous micro-emulsion phases. This system contains quaternary; water, n-dodecane, nitric acid, tributyl phosphate (TBP). This quaternary system has been shown to exhibit, under appropriate conditions, three coexisting phases: a light organic phase, an aqueous phase, and the so-called third phase. In this work, we focused on the coexistence of the light organic phase with the third phase using methods of molecular dynamics (MD) simulation and small-angle X-ray scattering (SAXS). Snapshots from the MD simulations as well as a cluster analysis of the organic and third phases revealed structures akin to bi-continuous micro-emulsion phases, with the polar species residing within a mesh, and with the surface of the mesh formed by amphiphilic TBP molecules. The non-polar n-dodecane molecules were observed in these snapshots to be outside this mesh. The only large-scale structural differences observed between the two phases were the dimensions of the mesh. Evidence for the correctness of these structures was provided by the results of SAXS studies, where the profiles obtained for both the organic and third phases agreed well with those calculated from simulation.
成田 弘一*; 前田 泰生*; 所 千晴*; 鈴木 智也*; 田中 幹也*; 元川 竜平; 塩飽 秀啓; 矢板 毅
Analytical Sciences, 33(11), p.1305 - 1309, 2017/11
Using -tetra-2-ethylhexyl-thiodiglycolamide (TEHTDGA) in -dodecane as the extractant, we compared the percentages of Pd(II) extracted from HCl and HBr solutions, and analyzed the structures of the Pd(II)-extractant complexes. TEHTDGA rapidly extracted Pd(II) from both HCl and HBr solutions, predominantly by formation of a 1:2 Pd(II)/TEHTDGA complex. The extractability of Pd(II) from HBr solution was inferior to that from HCl solution. FT-IR spectroscopy and EXAFS measurements indicated that two of the halide ions in the tetrachloro- or tetrabromopalladate(II) ions were replaced by the sulfur atoms of two TEHTDGA molecules. In the [PdBr(TEHTDGA)] complex, the Pd-S bond was shorter than the Pd-Br bond. We suggest that this bond length difference resulted in greater steric hindrance during coordination of TEHTDGA to the Pd(II) atom in the HBr system than in the HCl system, leading to the lower extractability in the HBr system.
久松 秀悟; 鈴木 伸一; 幸本 重男*; 岸川 圭希*; 山本 雄介*; 元川 竜平; 矢板 毅
Tetrahedron, 73(27-28), p.3993 - 3998, 2017/07
A sensory system incorporated with an amplification function was developed for detection of trace-level fluoride ions. This sensory system comprises two steps, namely, amplification, and chemiluminescence. These steps were linked with chemical reactions and were induced continuously. The process from amplification to chemiluminescence was accomplished in the system by using fluoride ions. The amplification was based on a self-immolative system, which permitted the detection of emissions even at low fluoride ion concentration for system in which chemiluminescence cannot be induced in the absence of fluoride ions. An optical ratio of the chemiluminescent compound and the amplifier was calculated for achieving efficient amplification.
関根 由莉奈; 元川 竜平; 香西 直文; 大貫 敏彦; 松村 大樹; 辻 卓也; 河崎 陸*; 秋吉 一成*
Scientific Reports (Internet), 7(1), p.2064_1 - 2064_8, 2017/05
成田 弘一*; 鈴木 智也*; 元川 竜平
日本金属学会誌, 81(4), p.157 - 167, 2017/04
Most of the refineries for platinum group metals (PGMs) in Japan have adopted solvent extraction methods for mutual separation of PGMs. Few effective extractants for industrial use have been found although some industrial processes were established in 1970s. Recently, some compounds have been reported as candidates for practical PGM extractants in addition to new concepts for PGM extraction mechanisms. In this review article, we present well-known PGM recovery processes based on solvent extraction, industrial extractants and their properties, and conventional extraction mechanism for PGMs. Additionally, we discuss recent interesting extraction systems (amide-type compounds and ionic liquid) and then introduce new extraction concepts based on the specific interactions at the outer-sphere of a metal complex in the organic phase.
前田 泰生*; 成田 弘一*; 所 千晴*; 田中 幹也*; 元川 竜平; 塩飽 秀啓; 矢板 毅
Separation and Purification Technology, 177, p.176 - 181, 2017/04
The separation properties of Pt(IV) over Fe(III) in HCl solutions using -2-ethylhexyl-bis(-di-2-ethylhexyl-ethylamide)amine (EHBAA) were investigated and then compared with those using the conventional extractant tri--octylamine (TOA). Also, the structural analyses of Pt(IV) in both of the aqueous (HCl solution) and organic (EHBAA in -dodecane-2-ethylhexanol solution) phases were performed with EXAFS spectroscopy. The extractability of Pt(IV) was much higher with EHBAA than with TOA in the studied HCl concentration range (0.2-0.8 M HCl); additionally, EHBAA selectively extracted Pt(IV) over Fe(III) under the condition of [EHBAA] 0.1 M and [HCl] 1 M. The Pt(IV) loading capacity of 0.1 M EHBAA was about 9.2 g/L (about 0.05 M). Most of the Pt(IV) extracted with 0.1 M EHBAA from 1 M HCl was stripped with 0.1 M NaOH; the co-extracted Fe(III) was selectively scrubbed with distilled water. The structural studies indicated that the Pt(IV) extracted with EHBAA from 1 M HCl formed an ion-pair complex, [PtCl](EHBAAH).
元川 竜平; 小林 徹; 遠藤 仁*; 池田 隆司; 矢板 毅; 鈴木 伸一; 成田 弘一*; 阿久津 和宏*; Heller, W. T.*
Journal of Nuclear Science and Technology, 53(8), p.1205 - 1211, 2016/08
This study uses small-angle neutron scattering (SANS) to elucidate the coordination structure of the complex of mono-acetyl substituted dibenzo-20-crown-6-ether (ace-DB20C6) with Cs. SANS profiles obtained for the complex of ace-DB20C6 and Cs (ace-DB20C6/Cs) in deuterated dimethyl sulfoxide indicated that Cs coordination resulted in a more compact structure than the free ace-DB20C6. The data were fit well with SANS profiles calculated using Debye function for scattering on an absolute scattering intensity scale. For this theoretical calculation of the scattering profiles, the coordination structure proposed based on a density functional theory calculation. Consequently, we conclude that the SANS analysis experimentally supports the proposed coordination structure of ace-DB20C6/Cs and suggests the following: (1) the complex of ace-DB20C6 and Cs is formed with an ace-DB20C6/Cs molar ratio of 1/1; (2) the two benzene rings of ace-DB20C6 fold around Cs above the center of the crown ether ring of ace-DB20C6.
元川 竜平; 谷口 竜王*; 熊田 高之; 飯田 優羽*; 青柳 翔太*; 佐々木 祐亮*; 桑折 道済*; 岸川 圭希*
Macromolecules, 49(16), p.6041 - 6049, 2016/08
We present a method for fabricating photonic crystals (PCs) by polymerization-induced microphase separation of block copolymers (BCPs). Molecular weight of BCP for PCs is so large that it has been difficult for conventional solution casting and annealing methods to complete the microphase separation to form periodically-ordered submicron structures. Our method overcomes the difficulty by inducing the micro phase separation and transitions during the polymerization, when the molecular weight of the BCPs is small enough for the microphase separation and transitions. The microphase-separated structure is then enlarged while maintaining the self-similarity. We succeeded in fabricating PCs with reflection wavelength m 1000 nm and a full width at half maximum = 0.05 m by living-radical bulk block-copolymerization of poly(methyl methacrylate)-block-polystyrene.
元川 竜平; 遠藤 仁*; 長尾 道弘*; Heller, W. T.*
Solvent Extraction and Ion Exchange, 34(5), p.399 - 406, 2016/07
We performed neutron polarization analysis (NPA) of extracted organic phases containing complexes, comprised of Zr(NO) and tri-n-butyl phosphate (TBP), which enabled decomposition of the intensity distribution of small-angle neutron scattering (SANS) into the coherent and incoherent scattering components. The coherent scattering intensity, containing structural information, and the incoherent scattering compete over a wide range of magnitude of scattering vector, , specifically when is larger than 1/, where is the radius of gyration of scatterer. Therefore, it is important to determine the incoherent scattering intensity exactly to perform an accurate structural analysis from SANS data when is small, such as the aforementioned extracted coordination species. Although NPA is the best method for evaluating the incoherent scattering component for accurately determining the coherent scattering in SANS, this method is not used frequently in SANS data analysis because it is technically challenging. In this study, we successfully demonstrated that experimental determination of the incoherent scattering using NPA is suitable for sample systems containing a small scatterer with a weak coherent scattering intensity, such as extracted complexes in biphasic solvent extraction system.
Mu, J.*; 元川 竜平; Williams, C. D.*; 阿久津 和宏*; 西辻 祥太郎*; Masters, A. J.*
Journal of Physical Chemistry B, 120(23), p.5183 - 5193, 2016/06
A refined model for tri--butyl phosphate (TBP), which uses a new set of partial charges generated from our ab initio density functional theory calculations, has been proposed in this study. Molecular dynamics simulations are conducted to determine the thermodynamic properties, transport properties, and the microscopic structures of liquid TBP, TBP/water mixtures, and TBP/-alkane mixtures. These results are compared with those obtained from four other TBP models, previously described in the literature. We conclude that our refined TBP model appears to be the only TBP model from this set that, with reasonable accuracy, can simultaneously predict the properties of TBP in bulk TBP, in organic diluents, and in aqueous solution. This new TBP model is thus appropriate for the simulation of liquid-liquid extraction systems in the nuclear extraction process, where one needs to simultaneously model TBP in both aqueous and organic phases. It is also promising for the investigation of the microscopic structure of the organic phase in these processes and for the characterization of third-phase formation, where TBP again interacts simultaneously with both polar and nonpolar molecules. Because the proposed TBP model uses OPLS-2005 Lennard-Jones parameters, it may be used with confidence to model mixtures of TBP with other species whose parameters are given by the OPLS-2005 force field.
元川 竜平; 遠藤 仁*; 横山 信吾*; 小川 紘樹*; 小林 徹; 鈴木 伸一; 矢板 毅
Langmuir, 30(50), p.15127 - 15134, 2014/12
The effect of cesium (Cs) adsorption on the mesoscopic structure of the clay minerals vermiculite and weathered biotite (WB) in suspensions was elucidated by small-angle X-ray scattering (SAXS). The clay minerals form multilayered structures and the Cs cations are strongly adsorbed in the interlayer space of the soil clays, in particular vermiculite and WB. SAXS was used to monitor the relationship between Cs adsorption at the clay interlayers and the structural changes at length scales from 0.1 to 100 nm. The variation in the distance between the neighboring clay sheets and the spatial arrangement of the clay sheets with and without Cs were clarified. Our quantitative analyses revealed that the number of stacked layers of pure vermiculite was decreased by Cs addition, whereas that of WB increased. Moreover, the average distance between the neighboring layers of vermiculite in suspension was larger than that of WB, which reflects the different conditions of Cs intercalation. These findings provide fundamental insights that are important for predicting the environmental fate of radioactive cesium in contaminated regions and for developing methods for extracting cesium from soil.
宮元 展義*; 島崎 浩太朗*; 山本 浩亮*; 新立 盛生*; 蒲池 雄一郎*; Bastakoti, B. P.*; 鈴木 孝宗*; 元川 竜平; 山内 悠輔*
Chemistry; A European Journal, 20(46), p.14955 - 14958, 2014/11
It is demonstrated that mesoporous silicas (MPSs) can be used as effective "topological cross-linkers" for poly(-isopropylacrylamide) (PNIPA) hydrogels to improve the mechanical property. Three-dimensional bicontinuous mesporous silica is found to effectively reinforce the PNIPA hydrogels, as compared to nonporous silica and two-dimensional hexagonally ordered mesoporous silica.
元川 竜平; 遠藤 仁*; 横山 信吾*; 西辻 祥太郎*; 小林 徹; 鈴木 伸一; 矢板 毅
Scientific Reports (Internet), 4, p.6585_1 - 6585_6, 2014/10
Following the Fukushima Daiichi nuclear disaster in 2011, Cs radioisotopes have been dispersed over a wide area. Most of the Cs has remained on the surface of the soil because Cs is strongly adsorbed in the interlayer spaces of soil clays, particularly vermiculite. We have investigated the microscopic structure of an aqueous suspension of vermiculite clay over a wide length scale (0.1-100 nm) by small-angle X-ray scattering. We determined the effect of the adsorption behavior of Cs on the structural changes in the clay. It was found that the abruption of the clay sheets was induced by the localization of Cs at the interlayer. This work provides important information for predicting the environmental fate of radioactive Cs in polluted areas, and for developing methods to extract Cs from the soil and reduce radioactivity.
Awual, M. R.; 小林 徹; 塩飽 秀啓; 宮崎 有史; 元川 竜平; 鈴木 伸一; 岡本 芳浩; 矢板 毅
Chemical Engineering Journal, 225, p.558 - 566, 2013/06
This study was investigated the trace lanthanide (Nd(III), Eu(III) and Yb(III)) sorption and recovery from wastewater streams by novel hybrid adsorbent. The experiments were investigated to determine the effects pH, ions selectivity and lanthanide ions coordination by XAFS spectra. The EXAFS data revealed that O and N donor atoms of the HA were strongly coordinated to lanthanide ions to form stable complexes. However, the bond distance of O donor atoms was shorter than N donor atoms.
Awual, M. R.; 小林 徹; 宮崎 有史; 元川 竜平; 塩飽 秀啓; 鈴木 伸一; 岡本 芳浩; 矢板 毅
Journal of Hazardous Materials, 252-253, p.313 - 320, 2013/05
The oxygen and nitrogen donor atoms containing Lewis base N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide (MePhPTA) ligand was synthesized and subsequently an adsorbent was prepared by direct immobilization onto mesoporous silica. The crystallography for the Sm-MePhPTA complex suggested that MePhPTA was strongly coordinated to Sm(III) with oxygen and nitrogen by forming a stable complex with two 5-membered rings. The data clarified that bond lengths between Sm(III) and amide oxygen (2.475 ) were shorter than Sm-N (2.662 ) in phenanthroline moiety indicating strong oxygen driven adsorbent.
元川 竜平; 谷口 竜王*; 佐々木 祐亮*; 榎本 勇人*; 村上 史泰*; 春谷 昌克*; 桑折 道済*; 中平 隆幸*
Macromolecules, 45(23), p.9435 - 9444, 2012/11
We have investigated the origin of a specific polymerization locus that yielded copolymer particles with a bimodal gel permeation chromatographic profile in the early stage of miniemulsion polymerization of styrene (St) with CDMAEMA. The formation of particles by miniemulsion polymerization using CDMAEMA was investigated as a function of the polymerization time (), and was compared with that using the non-polymerizable surfactant CTAB. GPC and elemental analysis indirectly predicted two different polymerization loci in the St/CDMAEMA/V50 polymerization system. Time-resolved SANS was used to directly observe and examine the specific polymerization loci in the miniemulsion polymerization solutions. The droplets formed in St/CDMAEMA/V50/PSt hydrophobe at the initial stage of the polymerization were not fully stabilized by CDMAEMA and poly(CDMAEMA-ran-St), and were found to build up the large aggregates. The spherical droplets were stabilized later in tp 20 min by forming a homogeneous dispersion in the water phase. Porod analysis of the power law scattering observed by SANS provided direct evidence for the specific polymerization loci, which appeared in the early stage of the polymerization system of St/CDMAEMA/V50/PSt hydrophobe on the surface of the droplet, and was the origin of the bimodal peaks in the GPC chromatogram.
坂本 直紀*; 島田 智子*; 元川 竜平; 小泉 智*
波紋, 22(2), p.172 - 177, 2012/05
Peptide amphiphile (PA) micelles are unique materials, whose morphologies are controlled by the peptide secondary structure as well as the length of the peptide and alkyl chains. The dynamics of the thermally-induced structural transition of our designed PA micelles was investigated by in situ small-angle neutron scattering (SANS) and Circular Dicroism (CD). The results revealed the time-evolution of the peptide secondary structure and the micellar morphology after temperature-jump. We propose the mechanism of these cooperative transitions: the change of the peptide secondary structure from a-helix and random coil to B-sheet induces the micellar structural transition from the spherical to the worm-like.