Assembly of Cobalt Layered Double Hydroxide on Cuprous Phosphide Nanowire with Strong Built‐In Potential for Accelerated Overall Water Splitting

Abstract Heterostructure plays an important role in boosting the overall water splitting (OWS) performance of nonprecious metal electrocatalysts. However, rational design and synthesis of semiconductor heterojunctions especially for Cu‐based ones as efficient bifunctional electrocatalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) still face challenges, and the in‐depth study of catalytic mechanisms is urgently needed. Herein, n‐type cobalt layered double hydroxide nanosheets are assembled on p‐type cuprous phosphide nanowire to form p‐n junction. This heterostructure with a strong built‐in potential ( E BI ) of 1.78 V provides enlarged electrochemical active surface area, enhanced active site, facilitated electron separation and transfer, and accelerated formation of superoxide radical. As expected, the heterogeneous electrocatalyst exhibits significantly improved activities for OWS, achieving an overpotential of 111 mV for HER and 221 mV for OER and an applied voltage of 1.575 V for OWS at 10 mA cm −2 in 1 m KOH. Moreover, the overpotentials are further decreased under visible light irradiation. This work represents a new insight into Cu‐based catalysts toward OWS and an approach based on E BI to design semiconductor heterostructure promising for renewable energy applications.