Kohei Kusada

Discovery of Face-Centered-Cubic Ruthenium Nanoparticles: Facile Size-Controlled Synthesis Using the Chemical Reduction Method

We report the first discovery of pure face-centered-cubic (fcc) Ru nanoparticles. Although the fcc structure does not exist in the bulk Ru phase diagram, fcc Ru was obtained at room temperature because of the nanosize effect. We succeeded in separately synthesizing uniformly sized nanoparticles of both fcc and hcp Ru having diameters of 2-5.5 nm by simple chemical reduction methods with different metal precursors. The prepared fcc and hcp nanoparticles were both supported on γ-Al2O3, and their catalytic activities in CO oxidation were investigated and found to depend on their structure and size.

Solid Solution Alloy Nanoparticles of Immiscible Pd and Ru Elements Neighboring on Rh: Changeover of the Thermodynamic Behavior for Hydrogen Storage and Enhanced CO-Oxidizing Ability

Pd(x)Ru(1-x) solid solution alloy nanoparticles were successfully synthesized over the whole composition range through a chemical reduction method, although Ru and Pd are immiscible at the atomic level in the bulk state. From the XRD measurement, it was found that the dominant structure of Pd(x)Ru(1-x) changes from fcc to hcp with increasing Ru content. The structures of Pd(x)Ru(1-x) nanoparticles in the Pd composition range of 30-70% consisted of both solid solution fcc and hcp structures, and both phases coexist in a single particle. In addition, the reaction of hydrogen with the Pd(x)Ru(1-x) nanoparticles changed from exothermic to endothermic as the Ru content increased. Furthermore, the prepared Pd(x)Ru(1-x) nanoparticles demonstrated enhanced CO-oxidizing catalytic activity; Pd0.5Ru0.5 nanoparticles exhibit the highest catalytic activity. This activity is much higher than that of the practically used CO-oxidizing catalyst Ru and that of the neighboring Rh, between Ru and Pd.

Hydrogen-Storage Properties of Solid-Solution Alloys of Immiscible Neighboring Elements with Pd

Rh and Ag are the elements neighboring Pd, which is well known as a hydrogen-storage metal. Although Rh and Ag do not possess hydrogen-storage properties, can Ag-Rh alloys actually store hydrogen? Ag-Rh solid-solution alloys have not been explored in the past because they do not mix with each other at the atomic level, even in the liquid phase. We have used the chemical reduction method to obtain such Ag-Rh alloys, and XRD and STEM-EDX give clear evidence that the alloys mixed at the atomic level. From the measurements of hydrogen pressure-composition isotherms and solid-state (2)H NMR, we have revealed that Ag-Rh solid-solution alloys absorb hydrogen, and the total amount of hydrogen absorbed reached a maximum at the ratio of Ag:Rh = 50:50, where the electronic structure is expected to be similar to that of Pd.

A Route for Phase Control in Metal Nanoparticles: A Potential Strategy to Create Advanced Materials

There is untapped potential for materials whose crystal structures are unobtainable in the bulk state. Several examples of such structures have been found in nanomaterials, and these materials exhibit unique properties that arise from their unique electronic states and surface structures. Here, recent developments in the syntheses of these nanomaterials and their unique properties, such as hydrogen-storage ability and catalytic activity, are summarized. Firstly, the syntheses and properties of novel solid-solution alloy nanoparticles in immiscible alloy systems such as Ag-Rh and Pd-Ru are introduced. Following this, the crystal structure control of nanoscale Ru is discussed. These unique alloy materials show enhanced properties and highlight the potential of phase control to be a new strategy for nanomaterial development.

The valence band structure of AgxRh1–x alloy nanoparticles

The valence band (VB) structures of face-centered-cubic Ag-Rh alloy nanoparticles (NPs), which are known to have excellent hydrogen-storage properties, were investigated using bulk-sensitive hard x-ray photoelectron spectroscopy. The observed VB spectra profiles of the Ag-Rh alloy NPs do not resemble simple linear combinations of the VB spectra of Ag and Rh NPs. The observed VB hybridization was qualitatively reproduced via a first-principles calculation. The electronic structure of the Ag0.5Rh0.5 alloy NPs near the Fermi edge was strikingly similar to that of Pd NPs, whose superior hydrogen-storage properties are well known.

Size dependence of structural parameters in fcc and hcp Ru nanoparticles, revealed by Rietveld refinement analysis of high-energy X-ray diffraction data.

To reveal the origin of the CO oxidation activity of Ruthenium nanoparticles (Ru NPs), we structurally characterized Ru NPs through Rietveld refinement analysis of high-energy X-ray diffraction data. For hexagonal close-packed (hcp) Ru NPs, the CO oxidation activity decreased with decreasing domain surface area. However, for face-centered cubic (fcc) Ru NPs, the CO oxidation activity became stronger with decreasing domain surface area. In comparing fcc Ru NPs with hcp Ru NPs, we found that the hcp Ru NPs of approximately 2 nm, which had a smaller domain surface area and smaller atomic displacement, showed a higher catalytic activity than that of fcc Ru NPs of the same size. In contrast, fcc Ru NPs larger than 3.5 nm, which had a larger domain surface area, lattice distortion, and larger atomic displacement, exhibited higher catalytic activity than that of hcp Ru NPs of the same size. In addition, the fcc Ru NPs had larger atomic displacements than hcp Ru NPs for diameters ranging from 2.2 to 5.4 nm. Enhancement of the CO oxidation activity in fcc Ru NPs may be caused by an increase in imperfections due to lattice distortions of close-packed planes and static atomic displacements.

Origin of the catalytic activity of face-centered-cubic ruthenium nanoparticles determined from an atomic-scale structure

The 3-dimensional (3D) atomic-scale structure of newly discovered face-centered cubic (fcc) and conventional hexagonal close packed (hcp) type ruthenium (Ru) nanoparticles (NPs) of 2.2 to 5.4 nm diameter were studied using X-ray pair distribution function (PDF) analysis and reverse Monte Carlo (RMC) modeling. Atomic PDF based high-energy X-ray diffraction measurements show highly diffuse X-ray diffraction patterns for fcc- and hcp-type Ru NPs. We here report the atomic-scale structure of Ru NPs in terms of the total structure factor and Fourier-transformed PDF. It is found that the respective NPs have substantial structural disorder over short- to medium-range order atomic distances from the PDF analysis. The first-nearest-neighbor peak analyses show a significant size dependence for the fcc-type Ru NPs demonstrating the increase in the peak height due to an increase in the number density as a function of particle size. The bond angle and coordination number (CN) distribution for the RMC-simulated fcc- and hcp-type Ru NP models indicated inherited structural features from their bulk counterparts. The CN analysis of the whole NP and surface of each RMC model of Ru NPs show the low activation energy packing sites on the fcc-type Ru NP surface atoms. Finally, our newly defined order parameters for RMC simulated Ru NP models suggested that the enhancement of the CO oxidation activity of fcc-type NPs was due to a decrease in the close packing ordering that resulted from the increased NP size. These structural findings could be positively supported for synthesized low-cost and high performance nano-sized catalysts and have potential application in fuel-cell systems and organic synthesis.

Dual Lewis Acidic/Basic Pd0.5Ru0.5–Poly(N‐vinyl‐2‐pyrrolidone) Alloyed Nanoparticle: Outstanding Catalytic Activity and Selectivity in Suzuki–Miyaura Cross‐Coupling Reaction

This article anticipates the development of dual Lewis acidic/basic alloyed nanoparticle (NP) of poly(N‐vinyl‐2‐pyrrolidone)‐stabilized Pd0.5Ru0.5 solid solution, revealing equivalent Pdδ+ and Ruδ− on the NP surface. This unsupported NP disclosed excellent catalytic efficiency with high turnover frequency, 15 000 h−1 in Suzuki–Miyaura cross‐coupling under notable drop of both Pd loading (0.08 mol %) and time (5 min) in air, attributed for its bifunctional acidic/basic modes. The bifunctional modes exposed the most interesting new reaction mechanism ascribed by the inductive effects of p‐substituents in arylboronic acid, accelerated reactivity by electron‐withdrawing group, revealing an opposite reactivity trend relative to other Pd‐based catalysts. Besides, the significant drops of Pd loading and reaction time impeded the metal leaching associated with no changes in NP surface composition/structure after the 3rd cycle (>99 % efficiency), revealing a line‐up for this NP in the environmental sustainability.

First-Principles Calculation, Synthesis and Catalytic Properties of Rh-Cu Alloy Nanoparticles

Abstract The first synthesis of pure Rh1−xCux solid‐solution nanoparticles is reported. In contrast to the bulk state, the solid‐solution phase was stable up to 750 °C. Based on facile density‐functional calculations, we made a prediction that the catalytic activity of Rh1−xCux can be maintained even with 50 at % replacement of Rh with Cu. The prediction was confirmed for the catalytic activities on CO and NOx conversions.

A Synthetic Pseudo-Rh: NO_x Reduction Activity and Electronic Structure of Pd-Ru Solid-solution Alloy Nanoparticles.

Rh is one of the most important noble metals for industrial applications. A major fraction of Rh is used as a catalyst for emission control in automotive catalytic converters because of its unparalleled activity toward NOx reduction. However, Rh is a rare and extremely expensive element; thus, the development of Rh alternative composed of abundant elements is desirable. Pd and Ru are located at the right and left of Rh in the periodic table, respectively, nevertheless this combination of elements is immiscible in the bulk state. Here, we report a Pd–Ru solid-solution-alloy nanoparticle (PdxRu1-x NP) catalyst exhibiting better NOx reduction activity than Rh. Theoretical calculations show that the electronic structure of Pd0.5Ru0.5 is similar to that of Rh, indicating that Pd0.5Ru0.5 can be regarded as a pseudo-Rh. Pd0.5Ru0.5 exhibits better activity than natural Rh, which implies promising applications not only for exhaust-gas cleaning but also for various chemical reactions.