The platinum-group metals (PGMs) are six neighboring elements in the periodic table of the elements. Each PGM can efficiently promote unique reactions, and therefore, alloying PGMs would create ideal catalysts for complex or multistep reactions that involve several reactants and intermediates. Thus, high-entropy-alloy (HEA) nanoparticles (NPs) of all six PGMs (denoted as PGM-HEA) having a great variety of adsorption sites on their surfaces could be ideal candidates to catalyze complex reactions. Here, we report for the first time PGM-HEA and demonstrate that PGM-HEA efficiently promotes the ethanol oxidation reaction (EOR) with complex 12-electron/12-proton transfer processes. PGM-HEA shows 2.5 (3.2), 6.1 (9.7), and 12.8 (3.4) times higher activity than the commercial Pd/C, Pd black and Pt/C catalysts in terms of intrinsic (mass) activity, respectively. Remarkably, it records more than 1.5 times higher mass activity than the most active catalyst to date. Our findings pave the way for promoting complex or multistep reactions that are seldom realized by mono- or bimetallic catalysts.

RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity.

A Ru/La0.5Ce0.5O1.75 catalyst pre-reduced at an unusually high temperature (650 °C) catalyses ammonia synthesis at a high rate under mild conditions.

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.

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.