Bimetal‐Incorporated Black Phosphorene with Surface Electron Deficiency for Efficient Anti‐Reconstruction Water Electrolysis

Abstract Surface reconstruction (SRC) is a common phenomenon and a promotion manner for Ni/Co‐based precatalysts during the water splitting process. However, the catalytic surface reconstruction will in turn complicate the streamlined prediction and modeling on the catalytic activity. Hence, the rational design of anti‐SRC catalysts is highly desirable, but challengeable. In this article, a series of affordable bimetal‐incorporated black phosphorene (BP) catalysts are constructed by an in situ electro‐exfoliation/insertion method for anti‐SRC water electrolysis. It is found that the bimetals (e.g., NiFe, NiPd) are of cationic and covalent incorporation with electron‐deficient state in few‐layer BP. The optimized bimetal‐BP structures present excellent and stable catalytic performances with low overpotentials in hydrogen evolution (HER, 53 mV, NiPd‐BP) and oxygen evolution (OER, 268 mV, NiFe‐BP) reactions at 10 mA cm⁻² in 1 m KOH. The anti‐SRC behaviors are elucidated by in situ Raman studies during HER/OER, probably due to the balanced electron transfer pathway on Ni sites. This research opens interesting possibilities for designing the anti‐SRC catalysts for efficient hydrogen production and authentic structure‐activity understandings.