記述言語：英語   出版者・発行元：Chemical Science  

Solid-solution alloys based on platinum group metals and p-block metals have attracted much attention due to their promising potential as materials with a continuously fine-tunable electronic structure. Here, we report on the first synthesis of novel solid-solution RuSn alloy nanoparticles (NPs) by electrochemical cyclic voltammetry sweeping of RuSn@SnOx NPs. High-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy maps confirmed the random and homogeneous distribution of Ru and Sn elements in the alloy NPs. Compared with monometallic Ru NPs, the RuSn alloy NPs showed improved hydrogen evolution reaction (HER) performance. The overpotentials of Ru0.94Sn0.06 NPs/C and Ru0.87Sn0.13 NPs/C to achieve a current density of 10 mA cm−2 were 43.41 and 33.19 mV, respectively, which are lower than those of monometallic Ru NPs/C (53.53 mV) and commercial Pt NPs/C (55.77 mV). The valence-band structures of the NPs investigated by hard X-ray photoelectron spectroscopy demonstrated that the d-band centre of RuSn NPs shifted downward compared with that of Ru NPs. X-ray photoelectron spectroscopy and X-ray absorption near-edge structure analyses indicated that in the RuSn alloy NPs, charge transfer occurs from Sn to Ru, which was considered to result in a downward shift of the d-band centre in RuSn NPs and to regulate the adsorption energy of intermediate Hads effectively, and thus enable the RuSn solid-solution alloy NPs to exhibit excellent HER catalytic properties.

DOI： 10.1039/d3sc06786f

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記述言語：英語   出版者・発行元：Nanoscale  

The properties of solids could be largely affected by their crystal structures. We achieved, for the first time, the phase control of solid-solution RuIn nanoparticles (NPs) from face-centred cubic (fcc) to hexagonal close-packed (hcp) crystal structures by hydrogen heat treatment. The effect of the crystal structure of RuIn alloy NPs on the catalytic performance in the hydrogen evolution reaction (HER) was also investigated. In the hcp RuIn NPs, enhanced HER catalytic performance was observed compared to the fcc RuIn NPs and monometallic Ru NPs. The intrinsic electronic structures of the NPs were investigated by valence-band X-ray photoelectron spectroscopy (VB-XPS). The d-band centre of hcp RuIn NPs obtained from VB-XPS was deeper than that of fcc RuIn NPs and monometallic Ru NPs, which is considered to enable the hcp RuIn NPs to exhibit enhanced HER catalytic performance.

DOI： 10.1039/d4nr00562g

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記述言語：英語   出版者・発行元：American Chemical Society (ACS)  

High-entropy oxide nanoparticles (HEO NPs) have been intensively studied because of their attractive properties, such as high stability and enhanced catalytic activity. In this work, for the first time, denary HEO NPs were successfully synthesized using a continuous supercritical hydrothermal flow process without calcination. Interestingly, this process allows the formation of HEO NPs on the order of seconds at a relatively lower temperature. The synthesized HEO NPs contained 10 metal elements, La, Ca, Sr, Ba, Fe, Mn, Co, Ru, Pd, and Ir, and had a perovskite-type structure. Atomic-resolution high-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements revealed homogeneous dispersion of the 10 metal elements. The obtained HEO NPs also exhibited a higher catalytic activity for the CO oxidation reaction than that of the LaFeO₃ NPs.

CiNii Research

記述言語：英語   出版者・発行元：Journal of the American Chemical Society  

High-entropy oxide nanoparticles (HEO NPs) have been intensively studied because of their attractive properties, such as high stability and enhanced catalytic activity. In this work, for the first time, denary HEO NPs were successfully synthesized using a continuous supercritical hydrothermal flow process without calcination. Interestingly, this process allows the formation of HEO NPs on the order of seconds at a relatively lower temperature. The synthesized HEO NPs contained 10 metal elements, La, Ca, Sr, Ba, Fe, Mn, Co, Ru, Pd, and Ir, and had a perovskite-type structure. Atomic-resolution high-angle annular dark-field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements revealed homogeneous dispersion of the 10 metal elements. The obtained HEO NPs also exhibited a higher catalytic activity for the CO oxidation reaction than that of the LaFeO3 NPs.

DOI： 10.1021/jacs.3c07351

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出版者・発行元：ACS Materials Letters  

We report the synthesis of novel RuIn solid-solution alloy nanoparticles (NPs) via the electrochemical cleaning of RuIn@InOx NPs. By alloying In to Ru, the RuIn NPs exhibited enhanced hydrogen evolution reaction (HER) activity compared with monometallic face-centered cubic (fcc) Ru NPs. Furthermore, the HER activity of RuIn NPs was comparable to that of commercial Pt catalysts. At a current density of 10 mA cm-2, RuIn NPs displayed a lower overpotential of 30.7 mV compared to monometallic fcc Ru NPs (57.8 mV) and commercial Pt NPs/C (34.1 mV). X-ray photoelectron spectroscopy and X-ray absorption near edge structure analysis revealed charge transfer from In to Ru in RuIn NPs. The results indicate that the alloying of In with Ru leads to beneficial intermetallic charge transfer, which efficiently modulates the desorption energy barrier to intermediate H* and enhances the intrinsic HER performance of monometallic fcc Ru NPs.

DOI： 10.1021/acsmaterialslett.3c01218

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記述言語：英語   出版者・発行元：Journal of the American Chemical Society  

Technetium (Tc), atomic number 43, is an element that humans cannot freely use even in the 21st century because Tc is radioactive and has no stable isotope. In this report, we present molybdenum-ruthenium-carbon solid-solution alloy (MoxRu1-xCy) nanoparticles (NPs) that are expected to have an electronic structure similar to that of technetium carbide (TcCy). MoxRu1-xCy NPs were synthesized by annealing under a helium/hydrogen atmosphere following thermal decomposition of metal precursors. The obtained NPs had a solid-solution structure in the whole composition range. MoxRu1-xCy with a cubic structure (down to 30 atom % Mo in the metal ratio) showed a superconducting state, and the transition temperature (Tc) increased with increasing Mo composition. The continuous change in Tc across that of TcCy indicates the continuous control of the electronic structure by solid-solution alloying, leading to pseudo-TcCy. Density functional theory calculations indicated that the synthesized Mo0.53Ru0.47C0.41 has a similar electronic structure to TcC0.41

DOI： 10.1021/jacs.3c06594

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記述言語：英語   出版者・発行元：Chemical Communications  

We first report the synthesis of B2-structured indium-platinum group metal high-entropy intermetallic nanoparticles (In-PGM HEI NPs). The synthesis was achieved by a wet-chemistry method and subsequent heat treatment. The crystal structure of these NPs is unique in the coexistence of completely orderly arranged indium and disorderly arranged PGMs.

DOI： 10.1039/d3cc02266h

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記述言語：英語   出版者・発行元：Journal of the American Chemical Society  

Multielement alloy nanoparticles have attracted much attention due to their attractive catalytic properties derived from the multiple interactions of adjacent multielement atoms. However, mixing multiple elements in ultrasmall nanoparticles from a wide range of elements on the periodic table is still challenging because the elements have different properties and miscibility. Herein, we developed a benchtop 4-way flow reactor for chemical synthesis of ultra-multielement alloy (UMEA) nanoparticles composed of d-block and p-block elements. BiCoCuFeGaInIrNiPdPtRhRuSbSnTi 15-element alloy nanoparticles composed of group IV to XV elements were synthesized by sequential injection of metal precursors using the reactor. This methodology realized the formation of UMEA nanoparticles at low temperature (66 °C), resulting in a 1.9 nm ultrasmall average particle size. The UMEA nanoparticles have high durability and activity for electrochemical alcohol oxidation reactions and high tolerance to CO poisoning. These results suggest that the multiple interactions of UMEA efficiently promote the multistep alcohol oxidation reaction.

DOI： 10.1021/jacs.3c03713

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記述言語：英語   出版者・発行元：Journal of the American Chemical Society  

High-entropy alloy nanoparticles (HEA NPs) emerged as catalysts with superior performances that are not shown in monometallic catalysts. Although many kinds of synthesis techniques of HEA NPs have been developed recently, synthesizing HEA NPs with ultrasmall particle size and narrow size distribution remains challenging because most of the reported synthesis methods require high temperatures that accelerate particle growth. This work provides a new methodology for the fabrication of ultrasmall and homogeneous HEA NPs using a continuous-flow reactor with a liquid-phase reduction method. We successfully synthesized ultrasmall IrPdPtRhRu HEA NPs (1.32 ± 0.41 nm), theoretically each consisting of approximately 50 atoms. This average size is the smallest ever reported for HEA NPs. All five elements are homogeneously mixed at the atomic level in each particle. The obtained HEA NPs marked a significantly high hydrogen evolution reaction (HER) activity with a very small 6 mV overpotential at 10 mA/cm-2 in acid, which is one-third of the overpotential of commercial Pt/C. In addition, although mass production of HEA NPs is still difficult, this flow synthesis can provide high productivity with high reproducibility, which is more energy efficient and suitable for mass production. Therefore, this study reports the 1 nm-sized HEA NPs with remarkably high HER activity and establishes a platform for the production of ultrasmall and homogeneous HEA NPs.

DOI： 10.1021/jacs.2c02755

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記述言語：英語   出版者・発行元：Chemical Communications  

Platinum-group-metal quinary RuRhPdIrPt alloy nanoparticles were synthesised with compositions slightly away from equimolar, and their crystal and electronic structures were investigated. Their lattice constant changed linearly with composition, while the d-band centre changed nonlinearly. Their catalytic activities for the hydrogen evolution reaction were not correlated with their d-band centre.

DOI： 10.1039/d2cc01866g

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記述言語：英語   出版者・発行元：Journal of the American Chemical Society  

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.

DOI： 10.1021/jacs.2c00583

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記述言語：英語   出版者・発行元：ACS Materials Au  

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.

DOI： 10.1021/acsmaterialsau.1c00048

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記述言語：英語   出版者・発行元：Journal of the American Chemical Society  

The compositional space of high-entropy-alloy nanoparticles (HEA NPs) significantly expands the diversity of the materials library. Every atom in HEA NPs has a different elemental coordination environment, which requires knowledge of the local electronic structure at an atomic level. However, such structure has not been disclosed experimentally or theoretically. We synthesized HEA NPs composed of all eight noble-metal-group elements (NM-HEA) for the first time. Their electronic structure was revealed by hard X-ray photoelectron spectroscopy and density function theory calculations with NP models. The NM-HEA NPs have a lower degeneracy in energy level compared with the monometallic NPs, which is a common feature of HEA NPs. The local density of states (LDOS) of every surface atom was first revealed. Some atoms of the same constituent element in HEA NPs have different LDOS profiles, whereas atoms of other elements have similar LDOS profiles. In other words, one atom in HEA loses its elemental identity and it may be possible to create an ideal LDOS by adjusting the neighboring atoms. The tendency of the electronic structure change was shown by supervised learning. The NM-HEA NPs showed 10.8-times higher intrinsic activity for hydrogen evolution reaction than commercial Pt/C, which is one of the best catalysts.

DOI： 10.1021/jacs.1c13616

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記述言語：英語   出版者・発行元：ACS Nano  

Compositional and structural arrangements of constituent elements, especially those at the surface and near-surface layers, are known to greatly influence the catalytic performance of alloyed nanoparticles (NPs). Although much research effort often focuses on the ability to tailor these important aspects in the design stage, their stability under realistic operating conditions remains a major technical challenge. Here, the compositional stability and associated structural evolution of a ternary iridium-palladium-ruthenium (Ir-Pd-Ru) nanoalloy at elevated temperatures have been studied using interrupted in situ scanning transmission electron microscopy and theoretical modeling. The results are based on a combinatory approach of statistical sampling at the sub-nanometer scale for large groups of NPs as well as tracking individual NPs. We find that the solid solution Ir-Pd-Ru NPs (?5.6 nm) evolved into a Pd-enriched shell supported on an alloyed Ir-Ru-rich core, most notably when the temperature exceeds 500 °C, concurrently with the development of expansive atomic strain in the outer surface and subsurface layers with respect to the core regions. Theoretically, we identify the weak interatomic bonds, low surface energy, and large atomic sizes associated with Pd as the key factors responsible for such observed features.

DOI： 10.1021/acsnano.1c10414

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