Enhancing the d/p‐Band Center Proximity with Amorphous‐Crystalline Interface Coupling for Boosted pH‐Robust Water Electrolysis

Abstract Rationalizing non‐precious pH‐robust electrocatalysts is a crucial priority and required for multi‐scenario hydrogen production customization. Herein, an amorphous–crystalline CoBO x /NiSe heterostructure is theoretically profiled and constructed for efficient and pH‐robust water electrolysis. The crystalline lattice confinement induces a CoCo bond shortening and a B‐site delocalization on amorphous CoBO x , resulting in a decreased d‐p band center difference (Δε d‐p ) toward the balanced intermediates adsorption/desorption. Accordingly, the CoBO x /NiSe heterostructure exhibits efficient and robust hydrogen/oxygen evolution reaction (HER/OER) catalytic activity in different electrolytes. Of particular note, it achieves ultralow overpotentials in both the beyond‐Pt HER (14.5 mV) and OER (229.1 mV) at 10 mA cm −2 under an alkaline electrolyte, and reaches an industrial‐level OER current density of 2 A cm −2 . Water electrolysis is stably delivered with a low η 10 voltage of 1.48 V. The incorporation of such d‐p orbitals at the amorphous–crystalline interface puts forward new opportunities in rationally designing advanced non‐precious electrocatalysts for water electrolysis.