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

Correlation between Geometrically induced oxygen octahedral tilts and multiferroic behaviors in BiFeO3 films

The equilibrium position of atoms in a unit cell is directly connected to crystal functionalities, e.g., ferroelectricity, ferromagnetism, and piezoelectricity. The artificial tuning of the energy landscape can involve repositioning atoms as well as manipulating the functionalities of perovskites (ABO3), which are good model systems to test this legacy. Mechanical energy from external sources accommodating various clamping substrates is utilized to perturb the energy state of perovskite materials fabricated on the substrates and consequently change their functionalities; however, this approach yields undesired complex behaviors of perovskite crystals, such as lattice distortion, displacement of B atoms, and/or tilting of oxygen octahedra. Owing to complimentary collaborations between experimental and theoretical studies, the effects of both lattice distortion and displacement of B atoms are well understood so far, which leaves us a simple question: Can we exclusively control the positions of oxygen atoms in perovskites for functionality manipulation? Here the artificial manipulation of oxygen octahedral tilt angles within multiferroic BiFeO3 thin films using strong oxygen octahedral coupling with bottom SrRuO3 layers is reported, which opens up new possibilities of oxygen octahedral engineering

Investigation of Local Structure and Enhanced Thermal Stability of Ir-Doped PdRu Nanoparticles for Three-Way Catalytic Applications

The local structure and thermal stability of newly synthesized PdRuIr and PdRu alloy nanoparticles (NPs) were studied using X-ray absorption fine structure spectroscopy (XAFS) and compared with those of Ru NPs. Pd K-edge XAFS reveals that a significant fraction of Pd segregates, forming metal NP clusters. In the PdRuIr NPs, a small fraction of Pd forms an alloy with Ir, whereas a majority phase is Ru–Ir alloy having the novel face-centered cubic structure. Apart from the distinct local surroundings, XAFS analysis revealed the presence of an anharmonic disorder in the PdRu and PdRuIr NPs. The previously observed enhanced thermal stability with Pd and Ir doping was investigated using temperature-dependent in situ XAFS. In the Ru NPs, an abrupt change in the near-edge features was observed at 673 K, which was gradually suppressed for PdRu and PdRuIr NPs. At this temperature, the dynamical fluctuations were more pronounced in the pure Ru NPs, helping to convert surface-adsorbed O$_2$ into the volatile RuO$_4$ phase, thereby leading to earlier evaporation of Ru. Dynamical fluctuation suppresses with alloying elements or gets extended to a higher temperature, helping to delay the RuO$_4$ formation process and enhancing the thermal stability of the PdRu and PdRuIr NPs in increasing order

Investigation of microstructure and hydrogen absorption properties of bulk immiscible AgRh alloy nanoparticles

Bimetallic alloy nanoparticles (NPs) exhibit superior catalytic and chemical storage properties relative to the monometallic NPs. Previously, it has been reported that bimetallic AgRh forms solid-solution alloy NPs that have unusual hydrogen storage properties not commonly observed in individual Ag and Rh NPs. Here, we use a combination of X-ray diffraction (XRD) and X-ray absorption fine structure spectroscopy (XAFS) techniques to investigate the microstructure and unique hydrogen absorption properties of bulk immiscible AgRh alloy NPs. XRD analysis reveals that the long-range structure of the alloy sample can be estimated as a single fcc phase with a slightly smaller lattice parameter than that of the bulk Ag and larger than that of bulk Rh. XAFS analysis reveals that charge transfer between Rh and Ag occurs in this interfacial region. The near-edge profile reveals a variety of local environments for Ag and Rh, including distinct atomic pair distances and disorder. The atomic pair distances were compressed around Ag and elongated around Rh. A substantial fraction of the sample is an alloy phase formed by mixing of nano/sub-nanosized domains of Rh and Ag NPs. Mixing at the atomic level mainly occurs in the interfacial region. Consequently, the interfacial region has an important influence over the microstructure and provides active sites for hydrogen absorption

Morphology evolution of self-organized porous structures in silicon surface

We have investigated the morphology evolution of silicon surface by laser irradiation. A pulsed ns-laser interaction with silicon in aqueous medium can produce self-organized microporous concave cell array structure without any chemicals and auxiliary equipment. Low radiant power was applied to the photo-induced non-thermal silicon surface modification. At the early stage, hemispherical patterns of 2 ∼ 3 µm were formed, maintaining a constant distance from each other without merging. Due to the thermal properties of water, subsurface heating proceeds under the silicon surface. The molten surface leads to the surface modulation to form subsided areas or expansions by nucleation and coalescence, resulting in the formation of a concave cone-shaped porous surface with a diameter of 10 ∼ 20 µm. The AFM reveals that the hierarchical hemispherical structures of two different scales are progressing simultaneously from the early stage. Keywords: Porous surface, Self-organization, LIPS

Effects of heat-treatment atmosphere and temperature on cobalt species in Co/Al2O3 catalyst for propane dehydrogenation

Co-based catalysts have attracted increasing attention as promising catalysts for propane dehydrogenation (PDH) because of their C–H bond activation ability. Co species in Co/Al2O3 are present in various forms, such as Co3O4, CoAl2O4, CoO, and metallic Co. However, the catalytic properties of the various Co species in PDH are unclear. In this work, we prepare Co/Al2O3 with different compositional distribution of Co species by heat-treating the supported Co precursor under O2, Ar, and H2 atmospheres at temperatures between 500 and 600 °C. H2-treated Co/Al2O3 results in superior performance compared to O2- and Ar-treated catalysts. This is attributed to the relatively high Co surface concentration and relatively high ratio of tetrahedral Co2+ stabilized in CoAl2O4 to the total Co species. A detailed study shows that both tetrahedral Co2+ and metallic Co in Co/Al2O3 are active for PDH, but the former is more selective.11Nsciescopu

Mechanism of Hydrogen Storage and Structural Transformation in Bimetallic PdPt Nanoparticles

The hydrogen storage capacity of Pd nanoparticles (NPs) decreases as the particles become smaller; however, this reduced capacity is ameliorated by addition of Pt. In the present work, the hydrogen storage mechanism and structural transformations of core (Pd)–shell (Pt) (CS) and solid-solution (SS) NPs during hydrogen absorption and desorption (PHAD) processes are investigated. In situ X-ray absorption spectroscopy measurements were performed to study the evolution of electronic and local structures around Pd and Pt during PHAD. Under ambient conditions, Pd and Pt have distinct local structures. The Pd atomic pairs are more strained in CS NPs than in SS NPs. A similar behavior has been seen in CS NPs after PHAD. The Pd K-edge extended X-ray absorption fine structure data indicate that in CS and SS NPs a substantial fraction of the signal derives from Pd–Pd atomic pairs, indicating that Pd clusters remain present even after PHAD. PHAD causes a rearrangement of the interfacial structure, which becomes homogeneously distributed. The higher coverage of active bimetallic sites results in a higher observed hydrogen storage capacity in the SS phase

Mechanism of Hydrogen Storage and Structural Transformation in Bimetallic Pd–Pt Nanoparticles

The hydrogen storage capacity of Pd nanoparticles (NPs) decreases as the particles become smaller; however, this reduced capacity is ameliorated by addition of Pt. In the present work, the hydrogen storage mechanism and structural transformations of core (Pd)–shell (Pt) (CS) and solid-solution (SS) NPs during hydrogen absorption and desorption (PHAD) processes are investigated. In situ X-ray absorption spectroscopy measurements were performed to study the evolution of electronic and local structures around Pd and Pt during PHAD. Under ambient conditions, Pd and Pt have distinct local structures. The Pd atomic pairs are more strained in CS NPs than in SS NPs. A similar behavior has been seen in CS NPs after PHAD. The Pd K-edge extended X-ray absorption fine structure data indicate that in CS and SS NPs a substantial fraction of the signal derives from Pd–Pd atomic pairs, indicating that Pd clusters remain present even after PHAD. PHAD causes a rearrangement of the interfacial structure, which becomes homogeneously distributed. The higher coverage of active bimetallic sites results in a higher observed hydrogen storage capacity in the SS phase