Evolution of amorphous ruthenium nanoclusters into stepped truncated nano-pyramids on graphitic surfaces boosts hydrogen production from ammonia.

Atomic-scale changes can significantly impact heterogeneous catalysis, yet their atomic mechanisms are challenging to establish using conventional analysis methods. By using identical location scanning transmission electron microscopy (IL-STEM), which provides quantitative information at the single-particle level, we investigated the mechanisms of atomic evolution of Ru nanoclusters during the ammonia decomposition reaction. Nanometre-sized disordered nanoclusters transform into truncated nano-pyramids with stepped edges, leading to increased hydrogen production from ammonia. IL-STEM imaging demonstrated coalescence and Ostwald ripening as mechanisms of nanocluster pyramidalization during the activation stage, with coalescence becoming the primary mechanism under the reaction conditions. Single Ru atoms, a co-product of the catalyst activation, become absorbed by the nano-pyramids, improving their atomic ordering. Ru nano-pyramids with a 2-3 nm footprint consisting of 3-5 atomic layers, ensure the maximum concentration of active sites necessary for the rate-determining step. Importantly, the growth of truncated pyramids typically does not exceed a footprint of approximately 4 nm even after 12 hours of the reaction, indicating their high stability and explaining ruthenium's superior activity on nanotextured graphitic carbon compared to other support materials. The structural evolution of nanometer-sized metal clusters with a large fraction of surface atoms is qualitatively different from traditional several-nm nanoparticles, where surface atoms are a minority, and it offers a blueprint for the design of active and sustainable catalysts necessary for hydrogen production from ammonia, which is becoming one of the critical reactions for net-zero technologies.