Directed Crystallization: Engineering Facet‐Specific High‐Entropy Alloy Nanocatalysts Toward Advanced Zinc‐Air Batteries

Precisely engineering crystallographic facets and dimensional architectures at the atomic scale is critical for unleashing the catalytic efficiency of high-entropy alloy (HEA) nanomaterials; however, the inherent complexity and atomic disorder of HEAs present significant synthetic challenges. Herein, we introduce an innovative directed crystallization strategy that integrates structure-directing agents (SDAs) and coordination solvents to kinetically steer precursor reduction pathways, enabling the synthesis of PtRuMoNiCoFe HEA nanocatalysts with tailored morphology dimensionality (0D-2D) and selectively exposed crystal facets. The (111)-facet-rich HEA nanowires (HEA@NWs) possess strain-engineered lattices with atomic step edges, undercoordinated sites, and defect-induced distortions that collectively promote localized electronic redistribution, thereby enhancing active-site density and accelerating interfacial electron transfer. Theoretical calculations reveal that (111) facet exposure elevates the d-band center, optimizing intermediate adsorption/desorption and significantly lowering the redox energy barrier. Consequently, the HEA@NWs exhibit an ultra-low redox overpotential gap (ΔE) of 0.68 V. As cathode catalysts in Zn-air batteries, the HEA@NWs deliver a high specific capacity of 797.8 mAh g_Zn ^-1 and exceptional cycling stability over 650 h at 10 mA cm^-2, substantially outperforming benchmark commercial catalysts (Pt/C + RuO₂, 350 h). This work establishes an advanced synthetic paradigm for facet-specific atomic-level design in HEA catalysts, underscoring their substantial potential for high-performance next-generation energy conversion technologies.