Unraveling the size-dependent effect of Ru-based catalysts on Ammonia synthesis at mild conditions

Identifying optimal Ru size in NH3 synthesis can improve reaction activity and maximize the utilization of Ru to reduce catalyst cost. However, previous researches are focused on large Ru particle size (≥2 nm) while that below 2 nm in NH3 synthesis is unclear. Here we synthesized a series of Rux/BaCeO3 with different Ru sizes (x = 1.1–3.0 nm) through size-controlled Ru colloid. With the decrease of Ru size, NH3 synthesis rate over Ru1.1/BaCeO3 increases to 19.4 mmol gcat−1h−1 at 400 °C and 1 MPa, which is 5.7 times that of Ru3.0/BaCeO3 and superior to most of Ru-based catalysts previously reported. It reveals that the reduction of Ru size enhances the generation of Ce3+ and oxygen vacancies in BaCeO3, which can donate electron to Ru centers and promote N2 dissociation. Moreover, the small Ru size enhances hydrogen spillover from Ru to BaCeO3 to alleviate hydrogen poisoning, resulting in efficient NH3 synthesis.