Ti‐Vacancy‐Mediated Construction of Ru 0 ‐O v ‐Ti 3+ Interfacial Sites for High‐Performance Ammonia Decomposition

ABSTRACT The exceptional ammonia (NH 3 ) decomposition performance of Ru‐based catalysts stems from its unique B5 site and optimized electronic properties, emphasizing “Interface Engineering” is the core strategy for its performance regulation. This work precisely modulates the geometric and electronic structures of Ru species by in situ constructing Ti vacancies in Titanium Silicalite‐1 (TS) zeolite. Characterization results revealed that construction of Ti vacancies in TS zeolite modulates the geometric configuration of Ru nanoparticles, improving its dispersion and B5 site concentration. More crucially, the construction of Ti vacancies enhances the metal‐support interactions between TS zeolite and Ru species, optimizing electron transfer between Ru and TS zeolite, tailoring the electronic structure of Ru site, and inducing the formation of more active Ru 0 –O v –Ti 3+ interface. In situ DRIFTS results demonstrate that Ru site primarily activates NH x intermediate to induce N‐H bond cleavage, and Ti 3+ site serves as a proton H* acceptor to induce Ti‐OH regeneration, collectively establishing efficient NH 3 decomposition catalytic cycle. DFT calculations further unravel the intrinsic electronic properties of Ru–O v –Ti 3+ structure and its thermodynamic predominance in each elementary step of the NH 3 decomposition. This work offers critical theoretical insights for rational design of high‐performance NH 3 decomposition catalysts.