Rational Design Strategy for High‐Valence Metal‐Driven Electronically Modulated High‐Entropy Co–Ni–Fe–Cu–Mo (Oxy)Hydroxide as Superior Multifunctional Electrocatalysts

Abstract Creating durable and efficient multifunctional electrocatalysts capable of high current densities at low applied potentials is crucial for widespread industrial use in hydrogen production. Herein, a Co–Ni–Fe–Cu–Mo (oxy)hydroxide electrocatalyst with abundant grain boundaries on nickel foam using a scalable coating method followed by chemical precipitation is synthesized. This technique efficiently organizes hierarchical Co–Ni–Fe–Cu–Mo (oxy)hydroxide nanoparticles within ultrafine crystalline regions (<4 nm), enriched with numerous grain boundaries, enhancing catalytic site density and facilitating charge and mass transfer. The resulting catalyst, structured into nanosheets enriched with grain boundaries, exhibits superior electrocatalytic activity. It achieves a reduced overpotential of 199 mV at 10 mA cm 2 current density with a Tafel slope of 48.8 mV dec 1 in a 1 m KOH solution, maintaining stability over 72 h. Advanced analytical techniques reveal that incorporating high‐valency copper and molybdenum elements significantly enhances lattice oxygen activation, attributed to weakened metal–oxygen bonds facilitating the lattice oxygen mechanism (LOM). Synchrotron radiation studies confirm a synergistic interaction among constituent elements. Furthermore, the developed high‐entropy electrode demonstrates exceptional long‐term stability under high current density in alkaline environments, showcasing the effectiveness of high‐entropy strategies in advancing electrocatalytic materials for energy‐related applications.