Ruthenium(0) nanoparticles supported on ceria (Ru-0/CeO2) were in situ generated from the reduction of ruthenium(III) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru-0/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru-0/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru-0/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru-0/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 +/- 0.1 degrees C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, E-a = 60 +/- 7 kJ mol(-1) for the nucleation and E-a = 47 +/- 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of E-a = 51 +/- 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.