La(FeCuMnMgTi)O3 High-Entropy Oxide Nanoparticles as Highly Efficient Catalysts for Solvent-Free Aerobic Oxidation of Benzyl Alcohol.

In this work, a solid-state method for the synthesis of perovskite La(FeCuMnMgTi)O3 high-entropy oxide (HEO) nanoparticles is detailed. Additionally, the high performance of these nanoparticles as catalysts in the aerobic and solvent-free oxidation of benzyl alcohol is demonstrated. The structural features of HEO nanoparticles are studied by X-ray diffraction and high-resolution transmission electron microscopy. The La(FeCuMnMgTi)O3 nanoparticles demonstrate excellent benzyl alcohol conversion rates and selectivity for benzaldehyde, reaching 10.6% conversion and 52.8% selectivity after reaction for only 4 h and ≤75.6% conversion after 24 h. In addition, the as-prepared HEO catalyst displays robust stability in benzyl alcohol oxidation. Density functional theory calculations demonstrate that the adsorption energy of benzaldehyde on the HEO surface is lower than that of the benzoic acid. This, in turn, hinders the gradual conversion of benzaldehyde to benzoic acid on the surface of HEO and retains benzaldehyde as the main product.

High-Entropy La(FeCuMnMgTi)O3 Nanoparticles as Heterogeneous Catalyst for CO2 Electroreduction Reaction.

In this work, La(FeCuMnMgTi)O3 HEO nanoparticles with a perovskite-type structure are synthesized and used in the electrocatalytic CO2 reduction reaction (CO2RR). The catalyst demonstrates high performance as an electrocatalyst for the CO2RR, with a Faradaic efficiency (FE) of 92.5% at a current density of 21.9 mA cm-2 under -0.75 V vs a saturated calomel electrode (SCE). Particularly, an FE above 54% is obtained for methyl isopropyl ketone (C5H10O, MIPK) at a partial current density of 16 mA cm-2, overcoming all previous works. Besides, the as-prepared HEO catalyst displays robust stability in the CO2RR. The excellent catalytic performance of La(FeCuMnMgTi)O3 is ascribed to the synergistic effect between the electronic effects associated with five cations occupying the high-entropy sublattice sites and the oxygen vacancies within the perovskite structure of the HEO. Finally, DFT calculations indicate that Cu plays a vital role in the catalytic activity of the La(FeCuMnMgTi)O3 HEO nanoparticles toward C2+ products.

A 3d-4d-5d High Entropy Alloy as a Bifunctional Oxygen Catalyst for Robust Aqueous Zinc-Air Batteries.

High entropy alloys (HEAs) are highly suitable candidate catalysts for oxygen evolution and reduction reactions (OER/ORR) as they offer numerous parameters for optimizing the electronic structure and catalytic sites. Herein, FeCoNiMoW HEA nanoparticles are synthesized using a solution-based low-temperature approach. Such FeCoNiMoW nanoparticles show high entropy properties, subtle lattice distortions, and modulated electronic structure, leading to superior OER performance with an overpotential of 233 mV at 10 mA cm-2 and 276 mV at 100 mA cm-2 . Density functional theory calculations reveal the electronic structures of the FeCoNiMoW active sites with an optimized d-band center position that enables suitable adsorption of OOH* intermediates and reduces the Gibbs free energy barrier in the OER process. Aqueous zinc-air batteries (ZABs) based on this HEA demonstrate a high open circuit potential of 1.59 V, a peak power density of 116.9 mW cm-2 , a specific capacity of 857 mAh gZn -1 , and excellent stability for over 660 h of continuous charge-discharge cycles. Flexible and solid ZABs are also assembled and tested, displaying excellent charge-discharge performance at different bending angles. This work shows the significance of 4d/5d metal-modulated electronic structure and optimized adsorption ability to improve the performance of OER/ORR, ZABs, and beyond.

Corrosion Resistance of Al0.5CoCrFeNiCuxAgy (x = 0.25, 0.5; y = 0, 0.1) High-Entropy Alloys in 0.5M H2SO4 Solution.

The electrochemical behavior of the as-cast Al0.5CoCrFeNiCuxAgy (x = 0.25, 0.5; y = 0, 0.1) high-entropy alloys (HEAs) in a 0.5M H2SO4 solution was studied. Polarization measurements were carried out in a standard three-electrode electrochemical cell at room temperature using a platinum counter electrode and a saturated silver chloride reference electrode. For Al0.5CoCrFeNiCu0.5 and Al0.5CoCrFeNiCu0.5Ag0.1, copper segregation along the grain boundaries was observed, which highly dissolved in the sulfuric acid solution and resulted in low corrosion resistance of the samples. Introducing Ag into Al0.5CoCrFeNiCu0.25 HEA led to the precipitation of a copper-silver eutectic structure, in which the copper regions were selectively dissolved in the sulfuric acid solution. Al0.5CoCrFeNiCu0.25 exhibited the best corrosion resistance with the corrosion current density of Icorr = 3.52 ± 0.02 µA/cm2, significantly superior to that of the Al0.5CoCrFeNi sample without copper and silver (Icorr = 6.05 ± 0.05 µA/cm2). Finally, the results indicated that suppressing elemental segregation by annealing or tailoring chemical composition is essential to improve the corrosion resistance of Al0.5CoCrFeNiCuxAgy HEAs.

CoFeNiMnZnB as a High-Entropy Metal Boride to Boost the Oxygen Evolution Reaction.

High-entropy materials offer numerous advantages as catalysts, including a flexible composition to tune the catalytic activity and selectivity and a large variety of adsorption/reaction sites for multistep or multiple reactions. Herein, we report on the synthesis, properties, and electrocatalytic performance of an amorphous high-entropy boride based on abundant transition metals, CoFeNiMnZnB. This metal boride provides excellent performance toward the oxygen evolution reaction (OER), including a low overpotential of 261 mV at 10 mA cm-2, a reduced Tafel slope of 56.8 mV dec-1, and very high stability. The outstanding OER performance of CoFeNiMnZnB is attributed to the synergistic interactions between the different metals, the leaching of Zn ions, the generation of oxygen vacancies, and the in situ formation of an amorphous oxyhydroxide at the CoFeNiMnZnB surface during the OER.