Modulation of Local Hydrogen Bonding for Highly Efficient Bi‐MOFs Photocatalyzed Fixation of N 2 in Aqueous Solution

作者：Tong Li, Huiying Yang, Meiyuan Wu, Zhongrui Chen, Zizhen Li, Yu Zheng, Zisheng Zhang, Chunhu LI, Xiangchao Meng · 发表于：Angewandte Chemie · 年份：2026 · DOI：10.1002/ange.202525232 · 被引用次数：1 · 研究领域：Advanced Photocatalysis Techniques、Ammonia Synthesis and Nitrogen Reduction、TiO2 Photocatalysis and Solar Cells

ABSTRACT For photocatalytic reduction of dinitrogen in aqueous solution, water plays an important role as not only a reactant to supply protons via the water oxidation reaction, but also a solvent, which cannot be neglected. At the interface between the catalyst surface and local water molecules, modulation of the hydrogen bonds (HBs) is critical for improving the production rate of ammonia. Herein, both roles (i.e., reactant and solvent) were balanced through the formation of an interfacial HB network between organic ligands of Bi‐MOFs and water with the aim of accelerating water oxidation to produce more protons and facilitating the adsorption of N 2 as well as the release of free water molecules. With this approach, the ammonia synthesis rate reached 258.86 µmol·g −1 ·h −1 at ambient conditions. As demonstrated, the empty 6p orbitals present in Bi 3+ (6s 2 6p 0 ), can accept electrons from the ligands due to the ligand‐to‐metal charge transfer (LMCT) effect. These electrons are then transferred to the π* antibonding orbitals of N 2 , thus significantly weakening the N≡N bond. The photogenerated holes on the ligands oxidize hydrogen‐bonded water molecules, producing more protons, which can further promote the critical process, namely the proton‐coupled electron transfer (PCET), for the multi‐step hydrogenation of N 2 . Therefore, the dynamic balance among N 2 adsorption and activation, proton supply capacity, and proton transfer was achieved through a local microenvironment...