Crystal Structure Control of Binary and Ternary Solid-Solution Alloy Nanoparticles with a Face-Centered Cubic or Hexagonal Close-Packed Phase

The crystal structure significantly affects the physical and chemical properties of solids. However, the crystal structure-dependent properties of alloys are rarely studied because controlling the crystal structure of an alloy at the same composition is extremely difficult. Here, for the first time, we successfully demonstrate the synthesis of binary Ru–Pt (Ru/Pt = 7:3) and Ru–Ir (Ru/Ir = 7:3) and ternary Ru–Ir–Pt (Ru/Ir/Pt = 7:1.5:1.5) solid-solution alloy nanoparticles (NPs) with well-controlled hexagonal close-packed (hcp) and face-centered cubic (fcc) phases, through the chemical reduction method. The crystal structure control is realized by precisely tunning the reduction speeds of the metal precursors. The effect of the crystal structure on the catalytic performance of solid-solution alloy NPs is systematically investigated. Impressively, all the hcp alloy NPs show superior electrocatalytic activities for the hydrogen evolution reaction in alkaline solution compared with the fcc alloy NPs. In particular, hcp-RuIrPt exhibits extremely high intrinsic (mass) activity, which is 3.1 (3.2) and 6.7 (6.9) times enhanced compared to that of fcc-RuIrPt and commercial Pt/C

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

Mixing of immiscible polymers using nanoporous coordination templates

混ざり合わないポリマーを完全に混ぜる手法を開発 -プラスチックの持つ機能を飛躍的に向上-. 京都大学プレスリリース. 2015-07-02.The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters

Solid-solution alloy nanoparticles of a combination of immiscible Au and Ru with a large gap of reduction potential and their enhanced oxygen evolution reaction performance

Au and Ru are elements that are immiscible in the bulk state and have the largest gap in reduction potential among noble metals. Here, for the first time, AuxRu₁₋x solid-solution alloy nanoparticles (NPs) were successfully synthesized over the whole composition range through a chemical reduction method. Powder X-ray diffraction and scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy showed that Au and Ru atoms are homogeneously mixed at the atomic level. We investigated the catalytic performance of AuxRu₁₋x NPs for the oxygen evolution reaction, for which Ru is well known to be one of the best monometallic catalysts, and we found that even alloying with a small amount of Au could significantly enhance the catalytic performance

Direct observation of the Ni stabilising effect in interfacial (Cu,Ni)6Sn5 intermetallic compounds

The polymorphic transformation in interfacial intermetallic compounds in three lead-free solder joints was investigated using in situ heating/isothermal/cooling observation techniques in high-voltage transmission electron microscopy (HVTEM). Here, the hexagonal η- to monoclinic η′-CuSn polymorphic transformation was visualised systematically through zone-axis electron diffraction patterns and real-space imaging. CuSn grains obtained in the as-reflowed solder joints that did not contain Ni (Sn–0.7Cu/Cu and Sn–3.0Ag–0.5Cu/Cu) show weak reflections in the diffraction patterns from the η′-CuSn. In Sn–0.7Cu–0.05Ni/Cu joints, no weak reflections were present in the diffraction patterns of the (Cu,Ni)Sn grains indicating the presence of Ni prevented the η- to η′-CuSn transformation. The movement of bend contours was also observed at around 186 °C in adjacent the grain boundaries in CuSn but not in the (Cu,Ni)Sn. We also uncover the origin of the weak reflections and confirm the superstructure of monoclinic η′-CuSn by obtaining atomic-resolution images within the areas from which the selected area diffraction patterns were obtained

Inter-element miscibility driven stabilization of ordered pseudo-binary alloy

元素間の混ざり方の違いを利用して新しい結晶構造の安定化に成功 --未踏の高機能材料開発への貢献に期待--. 京都大学プレスリリース. 2022-02-25.An infinite number of crystal structures in a multicomponent alloy with a specific atomic ratio can be devised, although only thermodynamically-stable phases can be formed. Here, we experimentally show the first example of a layer-structured pseudo-binary alloy, theoretically called Z3-FePd₃. This Z3 structure is achieved by adding a small amount of In, which is immiscible with Fe but miscible with Pd and consists of an alternate L10 (CuAu-type)-PdFePd trilayer and Pd–In ordered alloy monolayer along the c axis. First-principles calculations strongly support that the specific inter-element miscibility of In atoms stabilizes the thermodynamically-unstable Z3-FePd₃ phase without significantly changing the original density of states of the Z3-FePd₃ phase. Our results demonstrate that the specific inter-element miscibility can switch stable structures and manipulate the material nature with a slight composition change

Selective control of fcc and hcp crystal structures in Au–Ru solid-solution alloy nanoparticles

ナノ合金の画期的な結晶構造制御法の開発に成功 --革新的材料の創製へ--. 京都大学プレスリリース. 2018-02-06.Binary solid-solution alloys generally adopt one of three principal crystal lattices—body-centred cubic (bcc), hexagonal close-packed (hcp) or face-centred cubic (fcc) structures—in which the structure is dominated by constituent elements and compositions. Therefore, it is a significant challenge to selectively control the crystal structure in alloys with a certain composition. Here, we propose an approach for the selective control of the crystal structure in solid-solution alloys by using a chemical reduction method. By precisely tuning the reduction speed of the metal precursors, we selectively control the crystal structure of alloy nanoparticles, and are able to selectively synthesize fcc and hcp AuRu3 alloy nanoparticles at ambient conditions. This approach enables us to design alloy nanomaterials with the desired crystal structures to create innovative chemical and physical properties

Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeOx pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba2+, Ce3+ and La3+, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.</p

Co/Ba/La2O3 catalyst for ammonia synthesis under mild reaction conditions

Ruthenium catalysts may allow realization of renewable energy–based ammonia synthesis processes using mild reaction conditions (<400 °C, <10 MPa). However, ruthenium is relatively rare and therefore expensive. Here, we report a Co nanoparticle catalyst loaded on a basic Ba/La2O3 support and pre-reduced at 700 °C (Co/Ba/La2O3_700red) that showed higher ammonia synthesis activity at 350 °C and 1.0–3.0 MPa than two benchmark Ru catalysts, Cs+/Ru/MgO and Ru/CeO2. The synthesis rate of the catalyst at 350 °C and 1.0 MPa (19.3 mmol h−1g−1) was 8.0 times that of Co/Ba/La2O3_500red and 6.9 times that of Co/La2O3_700red. The catalyst showed activity at temperatures down to 200 °C. High-temperature reduction induced formation of a BaO-La2O3 nano-fraction around the Co nanoparticles, which increased turnover frequency, inhibited Co nanoparticle sintering, and suppressed ammonia poisoning. These strategies may also be appliable to nickel catalysts