Dual‐Intermetallic Heterostructure on Hierarchical Nanoporous Metal for Highly Efficient Alkaline Hydrogen Electrocatalysis

Abstract Constructing well‐defined active multisites is an effective strategy to break linear scaling relationships to develop high‐efficiency catalysts toward multiple‐intermediate reactions. Here, dual‐intermetallic heterostructure composed of tungsten‐bridged Co₃W and WNi₄ intermetallic compounds seamlessly integrated on hierarchical nanoporous nickel skeleton is reported as a high‐performance nonprecious electrocatalyst for alkaline hydrogen evolution and oxidation reactions. By virtue of interfacial tungsten atoms configuring contiguous multisites with proper adsorptions of hydrogen and hydroxyl intermediates to accelerate water dissociation/combination and column‐nanostructured nickel skeleton facilitating electron and ion/molecule transportations, nanoporous nickel‐supported Co₃W–WNi₄ heterostructure exhibits exceptional hydrogen electrocatalysis in alkaline media, with outstanding durability and impressive catalytic activities for hydrogen oxidation reaction (geometric exchange current density of ≈6.62 mA cm⁻²) and hydrogen evolution reaction (current density of ≈1.45 A cm⁻² at overpotential of 200 mV). Such atom‐ordered intermetallic heterostructure alternative to platinum group metals shows genuine potential for hydrogen production and utilization in hydroxide‐exchange‐membrane water electrolyzers and fuel cells.