Shape-dependent local strain in gold nanorods: data-driven atomic-resolution electron microscopy analysis

The local variation in inter-atomic distances, or local lattice strain often influences significantly material properties of nanoparticles. Strain measurement with ~1% precision is provided by recent atomic-resolution electron microscopy. However, the precision has been limited by noises in the experimental data. Here, we have applied one of the data-driven analyses, Gaussian process regression to predict true form of strain. The precision has been improved to be sub-percent of 0.2 % and more for detection of local strain. Rod-shaped nanoparticles have been revealed to contain characteristic lattice expansion ~+0.6 % around the subsurface cap tip area. The experimental results are reproduced by molecular dynamics simulations of the corresponding shaped atomic models. The strain peculiar to nanorods are explained in terms of curvature-dependent non-uniform surface stress due to shape anisotropy. The present results bring a hint to nanoscale engineering to optimize the strain in nanoparticles by shape control

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

Ni@onion-like carbon and Co@amorphous carbon: control of carbon structures by metal ion species in MOFs

We first report the facile synthesis of metal-carbon composites consisting of metal nanoparticles (NPs) and different types of carbon species: onion-like and amorphous carbon, Ni@onion-like carbon and Co@amorphous carbon. By simply changing the metal species in an isostructural metal-organic framework, thermal decompositions of MOF-74 directly afforded different types of metal NPs and carbon composites, which exhibited good electrical conductivity. In particular, the Ni@onion-like carbon, having a well-ordered carbon structure, had high electrical conductivity (sigma = 5.3 omega(-1) cm(-1) at 295 K), explained by a modified model of the Efros-Shklovskii variable range hopping

Three-dimensional imaging of a long-period stacking ordered phase in Mg₉₇Zn₁Gd₂ using high-voltage electron microscopy

Spatial configurations and lateral morphology of the 14H long-period stacking ordered (LPSO) phase have been studied by single tilt-axis electron tomography using high-voltage scanning transmission electron microscopy (STEM) operated at 1 MV. A "Quonset hut-like" lateral shape of the LPSO was found in a tomogram of a specimen as thick as 1.7 μ m. The reconstructed volume reveals spatial distribution of residual particulate precipitates of (Mg, Zn)3Gd phase 20-30 nm in diameters. The precipitates act as a source of solute elements for the formation and growth processes of 14H LPSO. 1 MV-STEM realizes enough resolution for imaging the morphology of LPSO as well as high electron transmittance (∼4.1 μ m) without any obvious electron irradiation damages on microstructures

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

Nano-scale dislocations induced by self-vacancy engineering yielding extraordinary n-type thermoelectric Pb0.96-yInySe

Nanostructuring has successfully enhanced thermoelectric performance for wide solid-state materials via embedding nano-scale particles, precipitates, or dislocations into the matrix to significantly lower the thermal conductivity. Herein, high-density dislocations are successfully introduced through engineering the off-stoichiometry ratio of cation atoms in Pb1-xSe. As examined by electron microscopy characterizations and phonon transport modeling studies, the existence of dense nano-scale dislocations in conjunction with grain boundaries and point defects lead to the strong wide-frequency phonon scatterings. Consequently, lattice thermal conductivity is significantly decreased in Pb1-xSe. Through doping In into the Pb0.96Se with an ultralow lattice thermal conductivity, the carrier concentration is tuned to reach the optimal level, which is confirmed by our modeling investigations. The synergistically obtained high-density of dislocations and the optimized carrier concentration lead to an extraordinary figure-of-merit of 1.6 in n-type Pb0.96-yInySe. This study demonstrates a natural way to induce high-density nano-scale dislocations by self-vacancy engineering, which extends the strategy of nanostructuring to broader materials for developing high-performance thermoelectric candidates

Kinetics of the β → α transformation of tin: role of α-tin nucleation

The influence of α-Sn nucleation on the kinetics of the β → α phase transformation are investigated, using in situ synchrotron powder X-ray diffraction (PXRD) with variable temperature control. In the entire thermal history of the α → β → α transformations, the population of α-Sn at the onset of the β → α transformation was varied by controlling the α → β transformation under isothermal conditions. The degree of α-Sn nucleation is found to have a correlation with the transformation kinetics of β → α. The growth component n is determined by both temperature and transformation time (fraction). By introducing an impingement factor, the transformation curves yielded a good fit to the modified Johnson-Mehl-Avrami-Kolmogorov (JMAK) model. At the commencement of the reaction, insufficient nucleation was found in samples subject to long anneals, and additional nucleation was required, at the kinetically optimal temperature of -45 °C