Synergistic Bimetallic Metal–Organic Frameworks with Engineered Hydrophobicity for Enhanced Nitrogen Reduction Toward Zinc–Nitrogen Batteries

Emerging zinc–nitrogen (Zn–N 2 ) batteries, which transform conventional electrically driven catalytic systems into electricity‐generating devices while simultaneously enabling ammonia electrosynthesis, are attracting increasing attention. As the core process, efficient nitrogen electrochemistry is essential for the performance of Zn–N 2 batteries. However, its operation in aqueous media is fundamentally constrained by the thermodynamic dominance of the hydrogen evolution reaction and the sluggish interfacial enrichment of inert nitrogen molecules. To address this bottleneck, this paper proposes a strategy to construct a hydrophobic microenvironment through bimetallic engineering, successfully preparing hydrophobic bimetallic metal–organic framework (MOF) composite Au/Ti–Zr–MOFs. This study shows that the synergistic effect of Ti and Zr bimetallic nodes not only induces lattice distortion, generating abundant defect sites that act as nitrogen‐trapping centers, but also modulates the surface electronic state to impart robust hydrophobicity. This engineered hydrophobic barrier actively repels interfacial water, effectively starving the active sites of protons and suppressing competitive hydrogen evolution. Consequently, the catalyst delivers an ammonia yield of 21.6 μg h −1 mg cat. −1 with a Faradaic efficiency of 28%. These findings establish bimetallic synergism as a robust mechanism for tailoring interfacial microenvironments, offering a generalizable paradigm for the rational design of high‐performance electrocatalytic systems for future metal–nitrogen batteries.