Superaerophobic Composite Coating of 2D g‐C ₃ N ₄ for Efficient Photo‐Assisted Water Splitting

ABSTRACT Photo‐assisted electrochemical (PAEC) water splitting represents a promising approach for efficient hydrogen and oxygen generation under solar illumination. However, catalyst delamination from the working electrode and blockage of electrochemically active sites due to gas bubble adhesion significantly hinder the performance. To overcome these issues, a 2D photocatalyst, graphitic carbon nitride (g‐C ₃ N ₄ ), was incorporated into a robust, highly bubble‐repellent composite coating on a porous nickel foam (NF) substrate. The resultant composite prevents g‐C ₃ N ₄ delamination from the electrode surface, while its intrinsic superaerophobicity enables rapid detachment of evolved gas bubbles. Furthermore, photoexcited charge carriers in g‐C ₃ N ₄ and its photothermal enhancement effectively assist water‐splitting reactions. Compared with conventional strategies involving direct photocatalyst coating on NF, with or without an additional bubble‐repellent layer, the proposed composite demonstrates a significantly improved PAEC performance. It exhibits a larger electrochemically active surface area, reduced overpotentials for both hydrogen and oxygen evolution reactions, and significantly improved gas evolution yields—enhancing hydrogen and oxygen production by 51% and 44%, respectively, at reduced applied potentials relative to bare NF under simulated solar illumination. This simple yet effective approach harnesses the cooperative influence of photoactive charge stimulation, localized photothermal enhancement, and optimized bubble dynamics in achieving stable, energy‐efficient photo‐assisted water splitting.