Construction of 2D‐Layered TiO ₂ Membrane for Enhanced Photocatalytic Hydrogen Production

Photocatalytic water splitting has emerged as a pivotal pathway toward sustainable hydrogen generation. Among potential catalysts, titanium dioxide (TiO 2 ) has garnered significant attention owing to its exceptional photoelectrochemical stability and tunable surface reactivity, positioning it as a benchmark material in this field. Herein, a bottom‐up layer‐by‐layer self‐assembly strategy is reported to construct 2D TiO 2 ‐based layered membranes (T‐Ms) with interconnected nanochannels. Precisely arranged TiO 2 nanosheets (T‐Ns) are engineered as building blocks to construct an integrated photocatalyst, where the porous architecture optimizes water molecule adsorption/desorption dynamics through confined nanospace effects. Systematic mechanistic studies demonstrate that the rational design of these nanochannels significantly enhances charge‐carrier mobility and light‐harvesting efficiency, thereby achieving a marked improvement in photocatalytic hydrogen‐evolution performance. The T‐Ms achieves a 1.8‐fold higher hydrogen‐evolution rate (393.0 μmol g −1 h −1 ) compared to solution‐dispersed TiO 2 nanoparticles (218.3 μmol g −1 h −1 ) under identical conditions. The T‐Ms‐30 sample is recommended as the primary experimental candidate. Notably, this sample maintains near‐constant of its initial activity over five consecutive 15 h cycles, demonstrating exceptional operational stability under continuous photocatalytic conditions. These results illuminate pathways toward sustainable hydrogen production and underscore the potential of nanostructured membrane architectures in practical energy applications.