Nanosilica stabilized rhodium(0) nanoparticles (Rh(0)/nanoSiO(2)), in situ formed from the reduction of rhodium(II) octanoate impregnated on the surface of nanosilica, are active catalyst in hydrogen generation from the methanolysis of ammonia borane at room temperature. Monitoring the hydrogen evolution enables us to follow the kinetics of nanoparticles formation. The resulting sigmoidal kinetic curves are analyzed by using the 2-step mechanism of the slow, continuous nucleation and autocatalytic surface growth. By using the temperature dependent kinetic data, we could calculate the activation energy for the nucleation and autocatalytic surface growth of rhodium(0) nanoparticles as well as for the catalytic methanolysis of ammonia borane. Rh(0)/nanoSiO(2) could be isolated and characterized by a combination of advanced analytical techniques including XRD, TEM, EDX, XPS, and N-2 adsorption-desorption. The results reveal that rhodium(0) nanoparticles are highly dispersed on nanosilica surface and have tunable particle size depending on the initial metal concentration. An increase in the mean particle size of rhodium(0) nanoparticles is observed when the initial metal concentration increases. Rh(0)/nanoSiO(2) are highly active and long lived catalyst in hydrogen generation from the methanolysis providing an exceptional initial turnover frequency of TOP=168 min(-1) (504 mm(-1) corrected for the surface atoms) at 25.0 +/- 0.5 degrees C, which is the highest value ever reported for rhodium catalysts. An inverse dependence of TOP on the initial rhodium concentration is observed and ascribed to the increasing size of rhodium(0) nanoparticles. Carbon disulfide poisoning and filtration experiments unequivocally demonstrate that rhodium(0) nanoparticles are the true heterogeneous catalyst in hydrogen generation from the methanolysis of ammonia borane. (C) 2015 Elsevier B.V. All rights reserved.