To understand the mechanism of the reaction catalyzed by high-entropy-alloy (HEA) electrocatalysts, it has become increasingly crucial to investigate the chemical nature of the adsorbed intermediate species on the metal sites. Herein, we proposed a high-entropy atomic environment regulation strategy to convert inactive to active sites for electrocatalysis. Integrating the low-electronegativity Mn and high-electronegativity Cu with Fe, Co, and Ni base metals to form a FeCoNiCuMn HEA nanoparticles (NPs) would drive the inactive Cu to electron-enriched active sites through the strong local electron interaction induced by electronegativity differences, thus availably reducing the adsorption energies of the reactants, intermediates and products and accordingly enhancing the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity of HEA. The HEA achieved excellent electrocatalytic activity for both the hydrogen evolution reaction (HER) (281 mV at 100 mA cm⁻²) and the oxygen evolution reaction (OER) (386 mV at 200 mA cm⁻²) and exhibited superior cycling stability, outperforming the benchmark Pt/C and IrO₂ catalysts. This work presents breakthroughs in the design of advanced HEA electrocatalysts for complex reactions.

The development of aqueous rechargeable zinc‐iodine (Zn‐I₂) batteries is still plagued by the polyiodide shuttle issue, which frequently causes batteries to have inadequate cycle lifetimes. In this study, quaternization engineering based on the concept of “electric double layer” is developed on a commercial acrylic fiber skeleton ($1.55–1.7 kg⁻¹) to precisely constrain the polyiodide and enhance the cycling durability of Zn‐I₂ batteries. Consequently, a high‐rate (1 C–146.1 mAh g⁻¹, 10 C–133.8 mAh g⁻¹) as well as, ultra‐stable (2000 cycles at 20 C with 97.24% capacity retention) polymer‐based Zn‐I₂ battery is reported. These traits are derived from the strong electrostatic interaction generated by quaternization engineering, which significantly eliminates the polyiodide shuttle issue and simultaneously realizes peculiar solution‐based iodine chemistry (I⁻/I₃⁻) in Zn‐I₂ batteries. The quaternization strategy also presents high practicability, reliability, and extensibility in various complicated environments. In particular, cutting‐edge Zn‐I₂ batteries based on the concept of derivative material (commercially available quaternized resin) demonstrate ≈100% capacity retention over 17 000 cycles at 20 C. This work provides a general and fresh insight into the design and development of large‐scale, low‐cost, and high‐performance zinc‐iodine batteries, as well as, other novel iodine storage systems.

The electrocatalytic nitrate (NO₃^-) reduction reaction (eNITRR) is a promising method for ammonia synthesis. However, its efficacy is currently limited due to poor selectivity, largely caused by the inherent complexity of the multiple-electron processes involved. To address these issues, oxygen-vacancy-rich LaFe_0.9M_0.1O_3-δ (M = Co, Ni, and Cu) perovskite submicrofibers have been designed from the starting material LaFeO_3-δ (LF) by a B-site substitution strategy and used as the eNITRR electrocatalyst. Consequently, the LaFe_0.9Cu_0.1O_3-δ (LF_0.9Cu_0.1) submicrofibers with a stronger Fe-O hybridization, more oxygen vacancies, and more positive surface potential exhibit a higher ammonia yield rate of 349 ± 15 μg h^-1 mg^-1_cat. and a Faradaic efficiency of 48 ± 2% than LF submicrofibers. The COMSOL Multiphysics simulations demonstrate that the more positive surface of LF_0.9Cu_0.1 submicrofibers can induce NO₃^- enrichment and suppress the competing hydrogen evolution reaction. By combining a variety of in situ characterizations and density functional theory calculations, the eNITRR mechanism is revealed, where the first proton-electron coupling step (*NO₃ + H⁺ + e^- → *HNO₃) is the rate-determining step with a reduced energy barrier of 1.83 eV. This work highlights the positive effect of cation substitution in promoting eNITRR properties of perovskites and provides new insights into the studies of perovskite-type electrocatalytic ammonia synthesis catalysts.