Contribution of Carbon Clusters to Ammonia Synthesis Over Ru‐Based Catalysts

Abstract Ammonia (NH 3 ) plays an important role in the development and evolution of Earth's life system. The extremely high bond energy (941 kJ mol −1 ) of N 2 hinder the conversion of N 2 to NH 3 under mild conditions. Meanwhile, clearly identifying the distribution of intermediates for NH 3 synthesis remains a huge challenge in the experiment. Herein, we anchored carbon clusters (C 60 or C 70 ) onto Ru catalysts supported on rare earth oxides, forming a class of Ru‐carbon cluster co‐catalysts that exhibit strong electronic metal‐carbon cluster interaction (EMCI). Carbon clusters function as an electron buffer that induced electron uptake from metallic Ru sites and concurrently provides electron feedback to Ru δ+ in a reversible manner, achieving a flexible balance of electron density at the Ru active sites. Moreover, H‐affinitive carbon clusters serve as the site for the adsorption, activation and migration of hydrogen. With Ru and carbon clusters synergistically bridged by hydrogen spillover, the Ru‐C 60 co‐catalyst exhibits an exceptionally high NH 3 synthesis rate and remarkable stability. Experimental provides direct evidence of the distribution and evolution of * N 2 H x ( x = 1∼3) intermediates, with the hydrogenation of * NH 2 to form *NH 3 identified as the rate‐determining step. This work paves the way for utilizing carbon clusters in important chemical reactions.