arXiv subjects

Shigeto Hirai

Publications and source records attributed to Shigeto Hirai.

6 recordsLinked to original sources

arXiv2025

Boron Clusters for Metal-Free Water Splitting

Electron-deficient boron clusters are identified as a fundamentally new class of oxygen evolution reaction (OER) catalysts, entirely free of transition metals. Selective sodium extraction from NaAlB14 and Na2B29 via high-pressure diffusion control introduces hole doping into B12 icosahedral frameworks, resulting in OER activity exceeding that of Co3O4 by more than an order of magnitude, and exceptional durability under alkaline conditions. B12 clusters are known for their superchaotropic character, which destabilizes hydrogen bonding in water. In this system, H2O, instead of OH-, preferentially adsorbs on the catalyst surface, suggesting a distinct OER pathway mediated by molecular water. This adsorption behavior contrasts with conventional transition-metal oxides and reflects the unique interfacial properties of the boron clusters. Density functional theory reveals unoccupied p orbitals and unique local electric fields at the cluster surface, both of which could promote the water activation. These findings suggest a paradigm shift in OER catalysis, in which the unique interaction between B12 clusters and water drives the reaction, replacing the conventional role of redox-active metals. Hole-doped boron clusters thus offer a promising platform for designing high-performance and durable water-splitting catalysts, opening new avenues for OER design beyond conventional transition-metal chemistry.

cond-mat.mtrl-sci↗

arXiv2025

Compositional Tuning in NaxAlB14 via Diffusion Control

A uniform Na distribution in NaxAlB14 was achieved using high-pressure diffusion control (HPDC), which promotes Na deintercalation through enhanced diffusion under high pressure, combined with post-annealing. NaxAlB14 with a non-stoichiometric Na composition is thermodynamically metastable, and conventional solid-state reactions with adjusted starting compositions typically result in the formation of stoichiometric NaAlB14 and side products. While HPDC alone typically leads to concentration gradients, intentionally halting the Na removal process before complete extraction, followed by annealing, enabled a uniform composition across the bulk. This allowed structural and electronic properties to be examined over a wide range of Na concentrations. As Na content decreased, electrical conductivity increased, and the optical band gap narrowed. NMR measurements showed an increase in the density of states at the Fermi level, consistent with DFT calculations predicting boron-related in-gap states. Boron vacancies at specific sites were found to generate deep levels near the band gap center, which can explain experimentally observed optical gap reduction. These results demonstrate that diffusion-controlling methods can be effectively applied to synthesize metastable compounds with tunable compositions in covalent frameworks. Furthermore, they provide a foundation for designing functional boride-based materials with adjustable electronic properties by controlling Na extraction and inducing defect formation.

cond-mat.mtrl-sci↗

arXiv2021

Fluorine solubility and superconducting properties of Sm(O,F)BiS$_2$ single crystals

Sm(O,F)BiS2 superconducting single crystals with various nominal F contents have been grown using KI-KCl flux. The solid solution limit of F at the O-site in Sm(O,F)BiS2 single crystals was approximately less than 20 at%. F concentrations of Sm(O,F)BiS2 single crystals were hardly controlled by nominal F contents. It suggests the existence of intrinsic stable phase. Superconductivity was shown at around 5 K. Superconducting transition temperature with zero resistivity were increased with increasing nominal F contents within less than 70 at% in O-site, despite similar F concentration and c-axis lattice constants.

cond-mat.supr-con↗

arXiv2018

Superconducting transition temperatures in the electronic and magnetic phase diagrams of Sr2VFeAsO3-delta, a superconductor

We elucidate the magnetic phases and superconducting transition temperatures (Tc) in Sr2VFeAsO3-delta (21113V), an iron-based superconductor with a thick-blocking layer fabricated from a perovskite-related transition metal oxide. At low temperatures (T < 37.1 K), 21113V exhibited a superconducting phase in the range 0.031 =< delta =< 0.145 and an antiferromagnetic (AFM) iron sublattice in the range 0.267 =< delta =< 0.664. Mixed-valent vanadium exhibited a dominant AFM phase in 0.031 =< delta =< 0.088, and a partial ferrimagnetic (Ferri.) phase in the range 0.124 =< delta =< 0.664. The Ferri. phase was the most dominant at a delta value of 0.267, showing an AFM phase of Fe at T < 20 K. Increasing the spontaneous magnetic moments reduced the magnetic shielding volume fraction due to the superconducting phase. This result was attributed to the magnetic phase of vanadium, which dominates the superconductivity of Fe in 21113V. The Tc-delta curve showed two maxima. The smaller and larger of Tc maxima occurred at delta = 0.073 and delta = 0.145, respectively; the latter resides on the phase boundary between AFM and the partial Ferri. phases of vanadium. 21113V is a useful platform for verifing new mechanisms of Tc enhancement in iron-based superconductors.

cond-mat.supr-con↗

arXiv2012

Giant atomic displacement induced by built-in strain in metastable Mn$_3$O$_4$

We present x-ray, neutron scattering and heat capacity data that reveal a coupled first-order magnetic and structural phase transition of the metastable mixed-valence post-spinel compound Mn$_3$O$_4$ at 210 K. Powder neutron diffraction measurements reveal a magnetic structure in which Mn$^{3+}$ spins align antiferromagnetically along the edge-sharing \emph{a}-axis, with a magnetic propagation vector k = [1/2, 0, 0]. In contrast, the Mn$^{2+}$ spins, which are geometrically frustrated, do not order until a much lower temperature. Although the Mn$^{2+}$ spins do not directly participate in the magnetic phase transition at 210 K, structural refinements reveal a large atomic shift at this phase transition, corresponding to a physical motion of approximately 0.25 Å even though the crystal symmetry remains unchanged. This "giant" response is due to the coupled effect of built-in strain in the metastable post-spinel structure with the orbital realignment of the Mn$^{3+}$ ion.

cond-mat.str-el↗

arXiv2012

Pressure-induced symmetry breaking in tetragonal CsAuI3

Results of in situ high pressure x-ray powder diffraction on the mixed valence compound Cs2Au(I)Au(III)I6 (CsAuI3) are reported, for pressures up to 21 GPa in a diamond anvil cell under hydrostatic conditions. We find a reversible pressure-induced tetragonal to orthorhombic structural transition at 5.5-6 GPa, and reversible amorphization at 12-14 GPa. Two alternative structures are proposed for the high-pressure orthorhombic phase, and are discussed in the context of a possible Au valence transition.

cond-mat.str-el↗