Constructing Interface‐Enhanced S‐Heterojunctions Via Surface Functionalization Strategies to Improve Photocatalytic Hydrogen Production Efficiency in Inorganic/Organic Composite Systems

S‐scheme heterojunctions play a crucial role in enhancing charge‐carrier separation efficiency and redox capability. However, the effect of S‐scheme heterojunction interface strength on carrier separation is still unclear. Herein, by functionalizing the surface of TiO 2 and employing in situ surface growth to construct an efficient transmission interface strategy. Characterization results indicate that the COF encapsulates TiO 2 and forms Ti‐N bonds at the interface, thereby strengthening the interface. The S‐scheme heterojunction after this strengthening process exhibits higher charge transport efficiency. The experimental results show that after enhancing the S‐scheme heterojunction interface, the photocatalytic hydrogen production rate can be reached to 38.15 mmol h −1 g −1 , which is 23.3 times that of the pristine TiO 2 . Furthermore, density functional theory (DFT) calculations revealed that the formation of the enhanced S‐scheme heterojunction interface can reduce the reaction barrier, enhance the H 2 O adsorption energy, and optimize reaction kinetics, thus significantly improving photocatalytic hydrogen evolution performance. Overall, this work introduces a novel strategy for heterojunction interface engineering and offers valuable insights into the design and optimization of high‐performance heterojunction photocatalysts.