Black Phosphorene: A Rising 2D Platform for Hydrogen Evolution Electrocatalysis

ABSTRACT Black phosphorene (BP), an emerging 2D material, possesses exceptional properties, including layer‐tunable bandgap, high carrier mobility, and anisotropic structure, which render it a compelling candidate electrocatalyst for the hydrogen evolution reaction (HER). However, its practical deployment is hindered by insufficient intrinsic activity and ambient instability. Starting from the HER fundamentals and structure advantages of BP, this review systematically dissects recent advances in multi‐scale design strategies for BP‐based electrocatalysts. We elucidate how layer thickness control, atomic doping, single‐atom anchoring, and heterostructure engineering synergistically optimize active sites and electronic structure, while passivation and encapsulation approaches enhance durability. By integrating in situ characterization and theoretical simulations, we decode the dynamic structural evolution and catalytic mechanism of BP‐based electrocatalysts. Finally, we outline the forward‐looking perspectives and insightful development directions, thereby establishing a comprehensive roadmap for designing efficient BP‐based catalysts.