Sharp Edges on Hierarchical Organic Polymers Accelerate Charge Transfer for Efficient Photocatalytic Hydrogen Production

ABSTRACT Organic polymer semiconductors have been regarded as a class of promising photocatalysts owing to their easy‐to‐tune properties, but the photocatalytic performance is limited by poor crystalline and low charge transfer efficiency. Herein, three‐dimensional (3D) crystalline organic polymer photocatalysts (denoted as DCS‐x) with sharp edges have been developed for photocatalytic hydrogen production through a coating confinement combined with molten salt etching method. It is found that sharp edges on crystalline 3D hierarchical architecture not only promote mass transfer, enhance light absorption, but also establish multidirectional charge transfer channels, and thereby boost photocatalytic H 2 evolution. As a result, the DCS‐1 shows the optimized photocatalytic H 2 evolution rate of 8.14 mmol h −1 g −1 with an apparent quantum yield of about 54% at 400 nm, which is about 3.1 times higher than that of DCS‐0 (2.64 mmol h −1 g −1 ), and even 38.8 times of enhancement of bulk g‐C 3 N 4 (0.21 mmol h −1 g −1 ). This work provides a new synthetic strategy for constructing crystalline 3D hierarchical organic polymer semiconductors for solar‐driven conversion.