Optimizing d‐p Orbital Hybridization with Abundant Unfilled Antibonding Orbital in Multi‐Metal Layered Double Hydroxide: Motivating Efficient Oxygen Evolving

Abstract Manipulating the electronic structure and coordination configuration of heterogeneous electrocatalyst is an advantageous strategy to motivate the intrinsic activity but remains challenging. Herein, guided by the theoretical mechanism of the d‐band center and valence‐bond theory, the high‐valence metal‐modulated nickel‐vanadium layered double hydroxides (M‐NiV LDH, M = Zr, and Mo) with interfacial oxygen bridge bonding structure are rationally designed and fabricated, affording a 3D vertically staggered and porous nanosheets array network. Benefitting from the abundant unfilled antibonding orbitals induced by the optimized Zr d‐orbital and O p‐orbital hybridization, the introduction of Zr site is beneficial to accelerate charge transfer kinetics and optimize the deprotonation of OH* as well as lower the O* → OOH* free energy. As a result, the as‐prepared Zr‐NiV LDH exhibits a promising oxygen evolution reaction performance with low overpotential and favorable long‐term stability. This work provides valuable insights into the design of electrocatalysts for electronic regulation and intrinsic activity improvement.