Denary High-Entropy Oxide Nanoparticles Synthesized by a Continuous Supercritical Hydrothermal Flow Process.

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.

Operando Spectroscopic Study of the Dynamics of Ru Catalyst during Preferential Oxidation of CO and the Prevention of Ammonia Poisoning by Pt.

Hydrogen is a promising clean energy source. In domestic polymer electrolyte fuel cell systems, hydrogen is produced by reforming of natural gas; however, the reformate contains carbon monoxide (CO) as a major impurity. This CO is removed from the reformate by a combination of the water-gas shift reaction and preferential oxidation of CO (PROX). Currently, Ru-based catalysts are the most common type of PROX catalyst; however, their durability against ammonia (NH3) as an impurity produced in situ from trace amounts of nitrogen also contained in the reformate is an important issue. Previously, we found that addition of Pt to an Ru catalyst inhibited deactivation by NH3. Here, we conducted operando XAFS and FT-IR spectroscopic analyses with simultaneous gas analysis to investigate the cause of the deactivation of an Ru-based PROX catalyst (Ru/α-Al2O3) by NH3 and the mechanism of suppression of the deactivation by adding Pt (Pt/Ru/α-Al2O3). We found that nitric oxide (NO) produced by oxidation of NH3 induces oxidation of the Ru nanoparticle surface, which deactivates the catalyst via a three-step process: First, NO directly adsorbs on Ru0 to form NO-Ruδ+, which then induces the formation of O-Ru n+ by oxidation of the surrounding Ru0. Then, O-Ru m+ is formed by oxidation of Ru0 starting from the O-Ru n+ nuclei and spreading across the surface of the nanoparticle. Pt inhibits this process by alloying with Ru and inducing the decomposition of adsorbed NO, which keeps the Ru in a metallic state.

Coreduction methodology for immiscible alloys of CuRu solid-solution nanoparticles with high thermal stability and versatile exhaust purification ability.

This study provides a coreduction methodology for solid solution formation in immiscible systems, with an example of a whole-region immiscible Cu-Ru system. Although the binary Cu-Ru alloy system is very unstable in the bulk state, the atomic-level well-mixed CuRu solid solution nanoparticles were found to have high thermal stability up to at least 773 K in a vacuum. The exhaust purification activity of the CuRu solid solution was comparable to that of face-centred cubic Ru nanoparticles. According to in situ infrared measurements, stronger NO adsorption and higher intrinsic reactivity of the Ru site on the CuRu surface than that of a pure Ru surface were found, affected by atomic-level Cu substitution. Furthermore, CuRu solid solution was a versatile catalyst for purification of all exhaust gases at a stoichiometric oxygen concentration.

Chemoselective hydrogenation of heteroarenes and arenes by Pd-Ru-PVP under mild conditions.

Monometallic (Pd, Ru or Rh) and bimetallic (Pd0.5-Ru0.5) alloy NPs catalysts were examined for the hydrogenation of quinoline. Pd-Ru alloy catalyst showed superior catalytic activity to the traditional Rh catalyst. The characterization of Pd0.5-Ru0.5 catalysts, HAADF-EDX mapping and XPS analysis suggested that the alloy state of PdRu catalysts remained unchanged in the recovered catalyst. Furthermore, the catalyst was highly selective for the hydrogenation of different arenes.

A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity.

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance-improved and cost-reduced solid-solution alloy nanoparticles of the Cu-Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cux Ru1-x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.

Solid-Solution Alloying of Immiscible Ru and Cu with Enhanced CO Oxidation Activity.

We report on novel solid-solution alloy nanoparticles (NPs) of Ru and Cu that are completely immiscible even above melting point in bulk phase. Powder X-ray diffraction, scanning transmission electron microscopy, and energy-dispersive X-ray measurements demonstrated that Ru and Cu atoms were homogeneously distributed in the alloy NPs. Ru0.5Cu0.5 NPs demonstrated higher CO oxidation activity than fcc-Ru NPs, which are known as one of the best monometallic CO oxidation catalysts.