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

Abstract 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 + RuO 2 , 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.