ナノ スケール ドウセキソウ マク ノ ネツショリ ニヨル ヒョウメン ケイジョウ ト ナイブ オウリョク ノ ヘンカ キョドウ

The specimen prepared in this study was multi-layer aluminum nitride and copper films deposited on thermal oxidation silicon by dc sputtering. Thermal stresses in the copper layers were investigated by ultra high X-rays of synchrotron radiation in the heating and cooling process. It found from the sin2Ψ diagrams of the multi-layered film that the copper layers consisted of crystal grains which had two different orientations. One was randomly orientation, and the other was {111} orientation. The FWHM of the diffraction from the {111}-oriented crystal grains was constant regardless of heating temperature. On the other hand, the FWHM of the diffraction from the randomly-oriented crystal grains was decreased with increasing heating temperature at 1st heating cycle and it became constant regardless of heating temperature after 1st heating cycle. The 2θ-sin2θ diagrams of the multi-layered film for the stress measurement showed non-linear. We could obtain thermal stresses in two different orientation crystal grains from the non-linear 2θ-sin2θ diagram at same time. For both crystal grains, the thermal stress differences between the 1st heating and the 1st cooling cycles were shown as a hysteresis loop. In the case of the 2nd thermal cycles, the thermal stresses changed linearly for both crystal grains. For the 1st heating cycle, the compressive thermal stress in the {111}-oriented crystal grains was larger than that in the randomly-oriented one

Controlling oxygen coordination and valence of network forming cations

Understanding the structure-property relationship of glass material is still challenging due to a lack of periodicity in disordered materials. Here, we report the properties and atomic structure of vanadium phosphate glasses characterized by reverse Monte Carlo modelling based on neutron/synchrotron X-ray diffraction and EXAFS data, supplemented by Raman and NMR spectroscopy. In vanadium-rich glass, the water durability, thermal stability and hardness improve as the amount of P2O5 increases, and the network former of the glass changes from VOx polyhedra to the interplay between VOx polyhedra and PO4 tetrahedra. We find for the first time that the coordination number of oxygen atoms around a V4+ is four, which is an unusually small coordination number, and plays an important role for water durability, thermal stability and hardness. Furthermore, we show that the similarity between glass and crystal beyond the nearest neighbour distance is important for glass properties. These results demonstrate that controlling the oxygen coordination and valence of the network-forming cation is necessary for designing the properties of glass

Efficient overall water splitting in acid with anisotropic metal nanosheets

超高効率な水の電気分解を実現するナノシート状合金触媒を開発 --再生可能エネルギーによる水素社会実現へ大きく貢献--. 京都大学プレスリリース. 2021-02-17.Water is the only available fossil-free source of hydrogen. Splitting water electrochemically is among the most used techniques, however, it accounts for only 4% of global hydrogen production. One of the reasons is the high cost and low performance of catalysts promoting the oxygen evolution reaction (OER). Here, we report a highly efficient catalyst in acid, that is, solid-solution Ru‒Ir nanosized-coral (RuIr-NC) consisting of 3 nm-thick sheets with only 6 at.% Ir. Among OER catalysts, RuIr-NC shows the highest intrinsic activity and stability. A home-made overall water splitting cell using RuIr-NC as both electrodes can reach 10 mA cm−2geo at 1.485 V for 120 h without noticeable degradation, which outperforms known cells. Operando spectroscopy and atomic-resolution electron microscopy indicate that the high-performance results from the ability of the preferentially exposed {0001} facets to resist the formation of dissolvable metal oxides and to transform ephemeral Ru into a long-lived catalyst

Phase Control of Solid-Solution Nanoparticles beyond the Phase Diagram for Enhanced Catalytic Properties

The crystal structure, which intrinsically affects the properties of solids, is determined by the constituent elements and composition of solids. Therefore, it cannot be easily controlled beyond the phase diagram because of thermodynamic limitations. Here, we demonstrate the first example of controlling the crystal structures of a solid-solution nanoparticle (NP) entirely without changing its composition and size. We synthesized face-centered cubic (fcc) or hexagonal close-packed (hcp) structured PdxRu₁–x NPs (x = 0.4, 0.5, and 0.6), although they cannot be synthesized as bulk materials. Crystal-structure control greatly improves the catalytic properties; that is, the hcp-PdxRu₁–x NPs exceed their fcc counterparts toward the oxygen evolution reaction (OER) in corrosive acid. These NPs only require an overpotential (η) of 200 mV at 10 mA cm⁻², can maintain the activity for more than 20 h, greatly outperforming the fcc-Pd₀.₄Ru₀.₆ NPs (η = 280 mV, 9 min), and are among the most efficient OER catalysts reported. Synchrotron X-ray-based spectroscopy, atomic-resolution electron microscopy, and density functional theory (DFT) calculations suggest that the enhanced OER performance of hcp-PdRu originates from the high stability against oxidative dissolution