Hydrophobic interface‐engineered Bi/Bi3TiNbO9 schottky photocatalyst for solar nitrogen fixation

Photocatalytic nitrogen fixation provides a sustainable alternative to the energy-intensive Haber–Bosch process, yet its efficiency is limited by poor N 2 solubility, weak adsorption, rapid charge recombination, and competing hydrogen evolution. reaction (HER). In this work, we introduce a synergistic interfacial strategy integrating Schottky junction construction and hydrophobic surface engineering to enhance photocatalytic N 2 fixation. Bi nanoparticles are in-situ anchored onto Bi 3 TiNbO 9 (BTNO) to construct Bi/BTNO Schottky junctions, facilitating directional electron transfer and accumulation at Bi active sites. Concurrently, surface hydrophobicity of Bi/BTNO is precisely tailored via 1-dodecanethiol modification, promoting N 2 enrichment at the reaction interface while effectively suppressing HER. The optimized 2C 12 S-1 % Bi/BTNO catalyst achieves an exceptional ammonia production rate of 25.83 μmol g -1 h −1 in pure water without sacrificial agents, outperforming pristine BTNO by 6.96-fold and unmodified Bi/BTNO by 2.85-fold. Photoelectrochemical measurements and in situ FTIR spectroscopy verify enhanced charge separation and an associative distal pathway for N 2 reduction. This work underscores the importance of interface microenvironment design in addressing kinetic and selectivity limitations, offering a versatile platform for efficient solar-driven nitrogen fixation.